KR20220128385A - Method for preparing cyclic carbonates having exocyclic vinylidene groups - Google Patents

Abstract

The present invention relates to a process for preparing a cyclic carbonate having an exocyclic vinylidene group by reacting propargyl alcohol with CO ₂ in the presence of a silver catalyst having at least one bulky ligand and a lipophilic carboxylate ligand, the method comprising: wherein after completion of the reaction the catalyst is separated from the cyclic carbonate by the use of two organic solvents of different polarities with miscibility disparities, wherein the silver catalyst is enriched in a less polar solvent and the cyclic carbonate is enriched in a more polar solvent.

Description

Method for preparing cyclic carbonates having exocyclic vinylidene groups

The present invention relates to a process for preparing a cyclic carbonate having an exocyclic vinylidene group by reacting propargyl alcohol with CO ₂ in the presence of a silver catalyst having at least one bulky ligand and a lipophilic carboxylate ligand, the method comprising: wherein after completion of the reaction the catalyst is separated from the cyclic carbonate by the use of two organic solvents of different polarities with miscibility disparities, wherein the silver catalyst is enriched in a less polar solvent and the cyclic carbonate is enriched in a more polar solvent.

Cyclic carbonates with exocyclic vinylidene groups are compounds useful, inter alia, for use as monomers in electrolytes for batteries as described in US 2013/0059178 or as monomers in polymer applications as described in WO 2011/157671 to be.

which does not have any other substituents other than the exocyclic vinylidene group (more precisely, the oxygen ring atom at the 1,3-position, the oxo group at the 2-position and the vinylidene group at the 4-position, cyclic carbonates (without substituents) are the corresponding primary propargyls using a silver catalyst with bulky ligands, as described in Organic Letters 2019, 21, 1422-1425 or WO 2019/034648. It is available through the reaction of an alcohol with CO ₂ . The reaction is carried out in an organic solvent such as dichloromethane or acetone. In the case of volatile products the product is separated from the catalyst via distillation and the catalyst can be recycled, as described in WO 2019/034648, which only requires the addition of fresh solvents and reagents to start a new reaction cycle . However, in the case of non-volatile or thermally unstable exo-vinylidene carbonate, this method cannot be applied and the product has to be separated from the catalyst via column chromatography, as also described in WO 2019/034648. In the case of industrial-scale processes, work-up of the reaction mixture via column chromatography is not economical due to its high cost; Moreover, the catalyst cannot be recycled in a simple manner.

See Chem. Commun. 2016, 52, 7830-7833], [ACS Sustainable Chem. Eng. 2019, 7, 5614-5619], [Green Chem. 2017, 19, 2936-2940] and [Journal of CO ₂ Utilization 2017, 22, 374-381] describe the reaction of tertiary propargyl alcohol with CO ₂ in the presence of a silver or copper catalyst and in the presence of an ionic liquid. The synthesis of 5,5-disubstituted cyclic carbonates having an exocyclic vinylidene group in the 4-position by Ionic liquids act as both solvents and bases. The product is separated from the reaction mixture by extraction with hexanes.

Ionic liquids are useful and versatile agents on a laboratory scale, but their cost makes them unsuitable for industrial scale processes. Moreover, this approach only works for non-polar cyclic carbonates that extract well into the hexane phase. The more polar products remain in the ionic liquid phase. If they are non-volatile or thermally unstable, they cannot be separated from the ionic liquid by distillation. As explained above, in the case of an industrial-scale process, the work-up of the reaction mixture via column chromatography is not economical due to its high cost; Moreover, the catalyst cannot be recycled in a simple manner.

It is therefore an object of the present invention as an economical process for the preparation of cyclic carbonates from primary propargyl alcohol and CO ₂ , which allows for a simple separation of the catalyst from the product, the use of ionic liquids as solvents and It was to provide a method that would not have to rely on such expensive means. In particular, the process should also enable the economical preparation of non-volatile or thermally unstable exo-vinylidene carbonate.

A process for the preparation of cyclic carbonate I selected from the group consisting of compounds of formula Ia, compounds of formula Ib and mixtures thereof, wherein the object is:

here

R ¹ is an organic radical;

It is achieved by a method comprising the steps of:

a) reacting propargyl alcohol of formula II with carbon dioxide:

wherein R ¹ is as defined above,

wherein the reaction is carried out in at least one organic solvent L1 or in a solvent mixture containing at least one organic solvent L1 and at least one organic solvent L2; wherein solvent L1 has a greater polarity than solvent L2, wherein solvents L1 and L2 have a miscibility gap at least at 20-30°C,

wherein the reaction is further carried out in the presence of a silver catalyst Ag1 comprising at least one bulky ligand and a carboxylate ligand,

wherein the bulky ligand is selected from the group consisting of a ligand of formula III and a ligand of formula IV:

here

D is P, As or Sb;

each R ² is independently an organic radical having 1 to 40 carbon atoms;

R ³ and R ⁴ are the same or different and are each an organic radical having 1 to 40 carbon atoms,

R ⁵ is an organic radical having 1 to 40 carbon atoms and may be different or the same as R ² present in ligand IV;

Z is a divalent bridge selected from -CR ⁷ =CR ⁸ -, -CR ⁷ =N-, -CR ⁷ R ⁹ -CR ⁸ R ¹⁰ - and -CR ⁷ R ⁹ -CR ⁸ R ¹⁰ -CR ¹¹ R ¹² - is a flag,

here

R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are independently of each other hydrogen or an organic radical having 1 to 40 carbon atoms; or

Two adjacent radicals R ⁷ and R ⁸ and/or R ¹⁰ and R ¹¹ together with the atoms connecting them have 4 to 40 carbon atoms and also as ring members the elements Si, Ge, N, P, O and S forming a monocyclic or polycyclic, substituted or unsubstituted, aliphatic or aromatic ring system which may contain at least one heteroatom selected from the group consisting of;

wherein the carboxylate ligand is according to formula (V):

here

R ⁶ is an organic radical having 1 to 40 carbon atoms;

b1) if step a) is not carried out in the presence of at least one solvent L2, adding solvent L2 to the reaction mixture obtained in step a);

b2) if step a) is carried out in the presence of at least one solvent L2: optionally adding solvent L2 to the reaction mixture obtained in step a);

c) subjecting the reaction mixture obtained in step a) or b1) or step b2) to phase separation to give a product phase containing cyclic carbonate I and at least one solvent L1, and a silver catalyst and at least one solvent obtaining a catalyst phase containing solvent L2; and

d), if desired, isolating the cyclic carbonate I from the product phase.

Naturally, the reaction mixture obtained in step a) is subjected to phase separation step c) only if a solvent mixture of L1 and L2 is used in step a) and if the optional step b2) is not carried out. If in step a) only L1 (and without L2) is used, the reaction mixture obtained in step b1) is subjected to phase separation step c). If a solvent mixture of L1 and L2 is used in step a) and if the optional step b2) has been carried out, the reaction mixture obtained in step b2) is subjected to a phase separation step c).

Justice

If a group R ¹ of compound II above or below (including A of compound II-bis or Poly or Y of compound II-poly) is defined as “as defined above” (where R ¹ is defined in relation to compound I) as), this does not necessarily imply that R ¹ remains unchanged in the reaction of compound II with CO ₂ . Some groups that may be present in R ¹ may react with CO ₂ to give compound I having a radical R ¹ that is different from R ¹ in starting compound II. For example, when R ¹ includes an oxiranyl group, some or all of them may react with CO ₂ under ring opening. However, in general, R ¹ is inert to the reaction conditions and is therefore identical in the starting compound II and the final compound I.

In this specification, when defining the variable R ^x of a given formula, the term radical is used interchangeably with the term group.

The term “halogen” denotes in each case fluorine, chlorine, bromine or iodine.

As used herein, the term “organic radical” refers to any radical having at least one carbon atom. Radicals may also contain heteroatoms such as halogen atoms, N, O, S, Si or Ge. "comprises" means that an organic radical may be substituted by a heteroatom-containing radical, may be interrupted by a heteroatom or heteroatom-containing group, and/or may be bound through a heteroatom or heteroatom containing group it means. However, in general, organic radicals are bound to the rest of the molecule through a carbon atom. Organic radicals are generally derived from individual molecules (an individual molecule is a molecule with a defined molecular weight, but not a molecular weight distribution as in the case of polymers), but the organic radical R ¹ can also be derived from polymers. In the latter case, ie when R ¹ is derived from a polymer, the starting compounds II generally contain more than one group -C≡C-CH ₂ OH. These groups may be attached to the polymer backbone either directly or via a linkage group. By way of example only, it contains a carboxyl group or carboxyl derivative susceptible to esterification (exchange) reaction, or contains an oxiranyl ring such as is present at a glycidyl moiety, or contains a chlorohydrin moiety or an isocyanate group (-NCO ) or a polymer or monomer containing another group in the side chain capable of reacting with an alcohol group is reacted with 1,4-butynediol or another diol having a propargyl alcohol group, so that R ¹ is a group -C≡C-CH in the side chain It is possible to provide (polymeric) compounds II, which are derived from polymers containing a large number of ₂ OH. If the monomer is reacted with 1,4-butynediol or another diol having a propargyl alcohol group, the polymer is of course obtained after polymerization of this monomer. In product I resulting from the reaction of the polymer with CO ₂ R ¹ is a plurality of cyclic carbonate groups bonded via an exocyclic vinylidene group (more precisely 1,3-dioxolan-2-one-4- one ring). Alternatively, the monomer may first be reacted with CO ₂ under the reaction conditions described above and below to provide a monomer containing the exo-vinylidene-bonded cyclic carbonate, which is subsequently polymerized. By way of example only, polyacrylic acid or polymethacrylic acid or polyacrylate or polymethacrylate susceptible to transesterification is esterified with 1,4-butynediol to form a repeating unit -[CH ₂ -CH(C(=O)) OCH ₂ C≡CH ₂ OH)]- or -[CH ₂ -C(CH ₃ )(C(=O)OCH ₂ C≡CH ₂ OH)]-; or a polyacrylate or polymethacrylate containing a -NCO group in the alcohol-derived portion of the ester (eg alcohol-derived portion derived from HO-CH ₂ CH ₂ -NCO) is 1,4-butynediol reacted by addition reaction with repeating units -[CH ₂ -CH(C(=O)O-CH ₂ CH ₂ -NH-C(=O)-O-CH ₂ C≡CH ₂ OH)]- or -[ CH ₂ -C(CH ₃ )(C(=O)O-CH ₂ CH ₂ -NH-C(=O)-O-CH ₂ C≡CH ₂ OH)]-; Alternatively, a polyacrylate or polymethacrylate containing a glycidyl moiety or a chlorohydrin moiety in the alcohol-derived portion of the ester may be reacted with 1,4-butynediol in an addition or substitution reaction. Alternatively, the corresponding acrylate or methacrylate monomers are first prepared by the esterification/addition/substitution reaction described above and then polymerized. In yet another alternative, the corresponding acrylate or methacrylate monomers (ie (meth)acrylates containing -C≡C-CH ₂ OH in the alcohol-derived moiety) are on a polymer having a suitable backbone. , for example on polyethylene or polypropylene polymers.

As used herein, the term “organic radical having from 1 to 40 carbon atoms” refers to any radical having at least one carbon atom. Radicals may also contain heteroatoms such as halogen atoms, N, O, S, Si or Ge. "comprises" means that an organic radical may be substituted by a heteroatom-containing radical, may be interrupted by a heteroatom or heteroatom-containing group, and/or may be bound through a heteroatom or heteroatom containing group it means. Examples thereof are C ₁ -C ₄₀ -alkyl radicals, fluorinated C ₁ -C ₁₀ -alkyl radicals, C ₁ -C ₁₂ -alkoxy radicals, 3 to 20 carbon atoms and at least one selected from N, O and S. Saturated, partially unsaturated or maximally unsaturated (including heteroaromatic) heterocyclic radicals containing heteroatoms as ring members, C ₆ -C ₄₀ -aryl radicals, C ₆ -C ₁₀ -fluoroaryl radicals, C ₆ -C ₁₀ -aryloxy radical, silyl radical having 3 to 24 carbon atoms, C ₂ -C ₄₀ -alkenyl radical, C ₂ -C ₄₀ -alkynyl radical, C ₇ -C ₄₀ -arylalkyl radical or C ₈ -C ₄₀ -arylalkenyl radical. The organic radicals are in each case derived from organic compounds. Thus, the organic compound methanol is in principle three different organic radicals having one carbon atom, namely methyl (H ₃ C-), methoxy (H ₃ CO-) and hydroxymethyl (HOC(H ₂ )-) ) can be created.

Aliphatic radicals are radicals that do not contain cycloaliphatic, aromatic or heterocyclic components. Examples thereof are alkyl, alkenyl, and alkynyl radicals. As used herein, when the term "aliphatic radical" is used without a prefix (C _n -C _m ), it is generally 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, in particular 1 to 20 carbons. denotes an aliphatic radical having atoms, in particular 1 to 10 or 1 to 6 or 1 to 4 carbon atoms. Naturally, alkenyl and alkynyl radicals have at least two carbon atoms.

Cycloaliphatic or cycloaliphatic radicals may contain one or more, for example, one or two, cycloaliphatic radicals; However, they do not contain aromatic or heterocyclic components. Examples thereof are cycloalkyl and cycloalkenyl radicals. As used herein, when the term "cycloaliphatic radical" is used without a prefix (C _n -C _m ), it generally has 3 to 40 carbon atoms, preferably 3 to 30 carbon atoms, in particular 3 to 20 carbon atoms. Denotes an aliphatic radical having carbon atoms, in particular 3 to 10 or 3 to 6 carbon atoms.

An aromatic radical or aryl (radical) is a mono-, bi- or polycyclic carbocyclic (ie, having no heteroatoms as ring members) aromatic radicals. One example of a monocyclic aromatic radical is phenyl. In a bicyclic aryl ring, two aromatic rings are condensed, ie they share two neighboring C atoms as ring members. One example of a bicyclic aromatic radical is naphthyl. In polycyclic aryl rings, three or more rings are condensed. Examples of polycyclic aryl radicals are phenanthrenyl, anthracenyl, tetracenyl, 1H-benzo[a]phenalenyl, pyrenyl and the like. However, "aryl" in the context of the present invention means that not all rings are aromatic, however, as long as at least one ring is aromatic; It also encompasses non- or polycyclic radicals, especially when the reactive site is present on the aromatic ring (or on the functional group attached thereto). Examples thereof include indanyl, indenyl, tetralinyl, 6,7,8,9-tetrahydro-5H-benzo[7]anulenyl, fluorenyl, 9,10-dihydroanthracenyl, 9,10- dihydrophenanthrenyl, 1H-benzo[a]phenalenyl, etc., and also ring systems in which not all rings are condensed, but are, for example, spiro-linked or bridged, such as benzonorbornyl. In particular, an aryl group has 6 to 30, more particularly 6 to 20, specifically 6 to 10 carbon atoms as ring members.

Mixed aliphatic-cycloaliphatic radicals contain at least one aliphatic radical and also at least one cycloaliphatic radical, wherein the bonding site with the rest of the molecule is located on the cycloaliphatic radical or on the aliphatic radical.

Mixed aliphatic-aromatic radicals contain at least one aliphatic radical and also at least one aromatic radical, wherein the bonding site with the rest of the molecule is located on the aromatic radical or on the aliphatic radical.

Mixed cycloaliphatic-aromatic radicals contain at least one cycloaliphatic radical and also at least one aromatic radical, wherein the bonding site with the rest of the molecule is located on the cycloaliphatic radical or on the aromatic radical.

Mixed aliphatic-cycloaliphatic-aromatic radicals contain at least one aliphatic radical, at least one cycloaliphatic radical and also at least one aromatic radical, wherein the bonding site with the remainder of the molecule is on the aliphatic radical or on the cycloaliphatic radical on or on an aromatic radical.

One or more non-adjacent groups -O-, -S-, -N(R ¹³ )-, -OC to the aliphatic residues of aliphatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic radicals (=O)-, -C(=O)-O-, -N(R ¹³ )-C(=O)-, -C(=O)-N(R ¹³ )-, -OC(=O) -O-, -OC(=O)-N(R ¹³ )-, -N(R ¹³ )-C(=O)-O- and/or -N(R ¹³ )-C(=O)-N If (R ¹³ )- is interrupted, this means, for example, that an aliphatic radical is a group -OR ^x , -SR ^x , -N(R ¹³ )-R ^x , -OC(=O)-R wherein R ^x is an aliphatic radical. ^x , -C(=O)-OR ^x , -N(R ¹³ )-C(=O)-R ^x , -C(=O)-N(R ¹³ )-R ^x , -OC(=O) -OR ^x , -OC(=O)-N(R ¹³ )-R ^x , -N(R ¹³ )-C(=O)-OR ^x and/or -N(R ¹³ )-C(=O) -N(R ¹³ )-R ^x .

At least one non-adjacent group to the cycloaliphatic residue of the cycloaliphatic, mixed aliphatic-cycloaliphatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic radicals -O-, -S-, -N(R ¹³ )- , -OC(=O)-, -C(=O)-O-, -N(R ¹³ )-C(=O)-, -C(=O)-N(R ¹³ )-, -OC( =O)-O-, -OC(=O)-N(R ¹³ )-, -N(R ¹³ )-C(=O)-O- and/or -N(R ¹³ )-C(=O )—N(R ¹³ )—, if interrupted, results in a saturated or partially unsaturated heterocyclic ring containing one or more of the above groups as ring members. To illustrate only such a ring, if the cycloaliphatic moiety is interrupted by a group -O-, -S- or -N(R ¹³ )-, this would be, for example, oxiranyl, thiiranyl, aziridinyl, oxeta. nyl, thietanyl, azetidinyl, furanyl, dihydrofuranyl, tetrahydrofuranyl, thienyl, dihydrothienyl, tetrahydrothienyl, pyrrolidinyl, pyrrolyl, pyrrolyl, pyranyl, di Hydropyranyl, tetrahydropyranyl, thiopyranyl, dihydrothiopyranyl, tetrahydrothiopyranyl, piperidinyl, dihydropyridinyl, tetrahydropyridinyl, pyridinyl and the like.

At least one non-adjacent group to the aromatic moiety of the aromatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic radicals -O-, -S-, -N(R ¹³ )-, -OC (=O)-, -C(=O)-O-, -N(R ¹³ )-C(=O)-, -C(=O)-N(R ¹³ )-, -OC(=O) -O-, -OC(=O)-N(R ¹³ )-, -N(R ¹³ )-C(=O)-O- and/or -N(R ¹³ )-C(=O)-N (R ¹³ )-, if interrupted, results in partially unsaturated or maximally unsaturated heterocyclic rings, including heteroaromatic rings.

An aliphatic bridging group is a divalent aliphatic radical. They do not contain any cycloaliphatic, aromatic or heterocyclic components. Examples thereof are alkylene, alkenylene and alkynylene radicals.

A cycloaliphatic bridging group is a divalent cycloaliphatic radical. A divalent cycloaliphatic radical may contain one or more, for example one or two, cycloaliphatic radicals. Cycloaliphatic radicals may be replaced by aliphatic radicals, but their bonding sites with the rest of the molecule they bridge are located on the cycloaliphatic radical.

An aromatic bridging group is a divalent aromatic radical. A divalent aromatic radical may contain one or more, for example, one or two aromatic radicals; However, they do not contain alicyclic or heterocyclic components. An aromatic radical may be replaced by an aliphatic radical, but both bonding sites with the rest of the molecule are located on the aromatic radical(s).

A mixed aliphatic-cycloaliphatic bridging group contains at least one divalent aliphatic radical and at least one divalent cycloaliphatic radical, wherein the two bonding sites with the rest of the molecule are presumably both on the cycloaliphatic radical(s) or Both are located on the aliphatic radical(s) or one on the aliphatic radical and the other on the cycloaliphatic radical.

A mixed aliphatic-aromatic bridging group contains at least one divalent aliphatic radical and at least one divalent aromatic radical, wherein the two bonding sites with the remainder of the molecule are possibly both on the aromatic radical(s) or both aliphatic one on the radical(s) or one on the aliphatic radical and the other on the aromatic radical.

A mixed aliphatic-cycloaliphatic-aromatic bridging group contains at least one divalent aliphatic radical, at least one divalent cycloaliphatic radical and at least one divalent aromatic radical, wherein the two bonding sites with the rest of the molecule are possibly two either on the cycloaliphatic radical(s) or both on the aliphatic radical(s) or both on the aromatic radical(s) or one on the aliphatic radical and the other on the cycloaliphatic or aromatic radical or one on the cycloaliphatic or aromatic radical one on the cycloaliphatic radical and the other on the aromatic radical.

The term "alkyl" generally has 1 to 40 ("C ₁ -C ₄₀ -alkyl") carbon atoms, preferably 1 to 30 ("C ₁ -C ₃₀ -alkyl") carbon atoms, more preferably preferably 1 to 20 ("C ₁ -C ₂₀ -alkyl") carbon atoms, in particular 1 to 10 ("C ₁ -C ₁₀ -alkyl") carbon atoms, in particular 1 to 6 ("C 1 -C 10 -alkyl") carbon atoms ₁ -C ₆ -alkyl") or saturated straight or branched with 1 to 4 ("C ₁ -C ₄ -alkyl") or 1 or 2 ("C ₁ -C ₂ -alkyl") carbon atoms Indicates an aliphatic hydrocarbon radical. C ₁ -C ₂ -alkyl is methyl or ethyl. Examples of C ₁ -C ₃ -alkyl are, in addition to those mentioned for C ₁ -C ₂ -alkyl, propyl and isopropyl. Examples of C ₁ -C ₄ -alkyl are, in addition to those mentioned for C ₁ -C ₃ -alkyl, butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl) or 1,1 -dimethylethyl (tert-butyl). Examples of C ₁ -C ₆ -alkyl are, in addition to those mentioned for C ₁ -C ₄ -alkyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1, 2-Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethyl propyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2-methylpropyl. Examples of C ₁ -C ₁₀ -alkyl are, in addition to those mentioned for C ₁ -C ₆ -alkyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl and positional isomers thereof. Examples of C ₁ -C ₂₀ -alkyl are, in addition to those mentioned for C ₁ -C ₁₀ -alkyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl , n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl and positional isomers thereof. Examples of C ₁ -C ₃₀ -alkyl are, in addition to those mentioned for C ₁ -C ₂₀ -alkyl, n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-penta cosyl, n-hexacosyl, n-octacosyl, n-nonacosyl, n-triacontyl and positional isomers thereof.

The term "fluorinated alkyl" generally has 1 to 30 ("fluorinated C ₁ -C ₃₀ -alkyl") carbon atoms, preferably 1 to 20 ("fluorinated C ₁ -C ₂₀ - alkyl"), in particular 1 to 10 ("fluorinated C ₁ -C ₁₀ -alkyl") carbon atoms, specifically 1 to 6 ("fluorinated C ₁ -C ₆ -alkyl") or saturated straight-chain or branched aliphatic hydrocarbons having 1 to 4 (“fluorinated C ₁ -C ₄ -alkyl”) or 1 or 2 (“fluorinated C ₁ -C ₂ -alkyl”) carbon atoms. As radicals, it indicates that some or all of the hydrogen atoms of these groups have been replaced by fluorine atoms. "Fluorinated methyl" is methyl in which one, two or three of the hydrogen atoms have been replaced by fluorine atoms. A “fluorinated C ₁ -C ₂ -alkyl” is an alkyl group having 1 or 2 carbon atoms (as mentioned above) wherein some or all of the hydrogen atoms of these groups are replaced by fluorine atoms. refers to A “fluorinated C ₁ -C ₃ -alkyl” is a straight-chain or branched alkyl group having from 1 to 3 carbon atoms (as mentioned above) wherein some or all of the hydrogen atoms of these groups are fluorine atoms. refers to being replaced by A “fluorinated C ₁ -C ₄ -alkyl” is a straight-chain or branched alkyl group having from 1 to 4 carbon atoms (as mentioned above), wherein some or all of the hydrogen atoms of these groups are fluorine atoms. refers to being replaced by A “fluorinated C ₁ -C ₆ -alkyl” is a straight-chain or branched alkyl group having 1 to 6 carbon atoms (as mentioned above) wherein some or all of the hydrogen atoms of these groups are fluorine atoms. refers to being replaced by A “fluorinated C ₁ -C ₈ -alkyl” is a straight-chain or branched alkyl group having from 1 to 8 carbon atoms (as mentioned above), wherein some or all of the hydrogen atoms of these groups are fluorine atoms. refers to being replaced by A “fluorinated C ₁ -C ₁₀ -alkyl” is a straight-chain or branched alkyl group having 1 to 10 carbon atoms (as mentioned above) wherein some or all of the hydrogen atoms of these groups are fluorine atoms. In a way that refers to what has been replaced by , etc. Examples of fluorinated methyl are fluoromethyl, difluoromethyl and trifluoromethyl. Examples of fluorinated C ₁ -C ₂ -alkyl are fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2, 2,2-trifluoroethyl, or pentafluoroethyl. Examples of fluorinated C ₁ -C ₃ -alkyl are, in addition to those mentioned for fluorinated C ₁ -C ₂ -alkyl, 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 1,1-difluoropropyl, 2,2-difluoropropyl, 1,2-difluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, heptafluoro propyl, 1,1,1-trifluoropropyl-2-yl, heptafluoropropyl, and the like. Examples of fluorinated C ₁ -C ₄ -alkyl are, in addition to those mentioned for fluorinated C ₁ -C ₃ -alkyl, 4-fluorobutyl, nonafluorobutyl, heptadecafluorooctyl and the like .

In perfluorinated alkyls, all hydrogen atoms are replaced by fluorine atoms. Examples thereof are trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, heptadecafluorooctyl and the like.

The term "haloalkyl" (also expressed as "partially or fully halogenated alkyl") generally has 1 to 30 ("fluorinated C ₁ -C ₃₀ -alkyl") carbon atoms, preferably 1 to 20 carbon atoms. (“fluorinated C ₁ -C ₂₀ -alkyl”) carbon atoms, in particular 1 to 10 (“fluorinated C ₁ -C ₁₀ -alkyl”) carbon atoms, in particular 1 to 6 (“fluorine”) rinsed C ₁ -C ₆ -alkyl”) or 1 to 4 (“fluorinated C ₁ -C ₄ -alkyl”) or 1 or 2 (“fluorinated C ₁ -C ₂ -alkyl”) saturated straight-chain or branched aliphatic hydrocarbon radicals having carbon atoms, wherein some or all of the hydrogen atoms of these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and/or bromine . "C ₁ -C ₂ -haloalkyl" is an alkyl group having 1 or 2 carbon atoms (as mentioned above), wherein some or all of the hydrogen atoms of these groups are halogen atoms as mentioned above, in particular refers to replaced by fluorine, chlorine and/or bromine. "C ₁ -C ₃ -haloalkyl" is a straight chain or branched alkyl group having from 1 to 3 carbon atoms (as mentioned above), wherein some or all of the hydrogen atoms of these groups are as mentioned above. refers to those replaced by halogen atoms, especially fluorine, chlorine and/or bromine. “C ₁ -C ₄ -haloalkyl” is a straight-chain or branched alkyl group having from 1 to 4 carbon atoms (as mentioned above), wherein some or all of the hydrogen atoms of these groups are as mentioned above. refers to those replaced by halogen atoms, especially fluorine, chlorine and/or bromine. "C ₁ -C ₆ -haloalkyl" is a straight chain or branched alkyl group having 1 to 6 carbon atoms (as mentioned above), wherein some or all of the hydrogen atoms of these groups are as mentioned above. refers to those replaced by halogen atoms, especially fluorine, chlorine and/or bromine. Examples of C ₁ -C ₂ -haloalkyl are chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chloro Difluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2- chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl or pentafluoroethyl. Examples of C ₁ -C ₃ -haloalkyl are, in addition to those mentioned for C ₁ -C ₂ -haloalkyl, 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 1,1- Difluoropropyl, 2,2-difluoropropyl, 1,2-difluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, heptafluoropropyl, 1, 1,1-trifluoroprop-2-yl, 3-chloropropyl, and the like. Examples of C ₁ -C ₄ -haloalkyl are, in addition to those mentioned for C ₁ -C ₃ -haloalkyl, 4-chlorobutyl and the like.

Strictly speaking, the term "alkenyl" generally has 2 to 40 ("C ₂ -C ₄₀ -alkenyl") carbon atoms, preferably 2 to 30 ("C ₂ -C ₃₀ -alkenyl") carbon atoms. of carbon atoms, more preferably 2 to 20 ("C ₂ -C ₂₀ -alkenyl") carbon atoms, in particular 2 to 10 ("C ₂ -C ₁₀ -alkenyl") carbon atoms, specifically monounsaturated (i.e., 1 C-C double bond) having 2 to 6 ("C ₂ -C ₆ -alkenyl") or 2 to 4 ("C ₂ -C ₄ -alkenyl") carbon atoms as containing) straight-chain or branched aliphatic hydrocarbon radical, wherein the CC double bond may be present at any position. However, as used herein, the term also refers to an "alkapolyenyl" group, ie generally from 4 to 40 ("C ₄ -C ₄₀ -alkapolyenyl") carbon atoms, preferably is 4 to 30 ("C ₄ -C ₃₀ -alkapolyenyl") carbon atoms, more preferably 4 to 20 ("C ₄ -C ₂₀ -alkapolyenyl") carbon atoms, in particular straight-chain or branched aliphatic hydrocarbon radicals having 4 to 10 ("C ₄ -C ₁₀ -alkapolyenyl") carbon atoms, and two or more conjugated or isolated, but not consecutive, C-C double bonds; encompasses Examples of C ₂ -C ₃ -alkenyl in the strict sense (only one CC double bond) are ethenyl, 1-propenyl, 2-propenyl or 1-methylethenyl. Examples of C ₂ -C ₄ -alkenyl in the strict sense (only one CC double bond) are ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl , 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl and 2-methyl-2-propenyl. Examples of C ₂ -C ₆ -alkenyl in the strict sense (only one CC double bond) are ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl , 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-phen tenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2- Methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2 -propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2 -Hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl- 1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4 -pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2- Dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl , 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl -1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1- Butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl -2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, and the like. Examples of C ₂ -C ₁₀ -alkenyl in the strict sense (only one CC double bond) are, in addition to the examples mentioned for C ₂ -C ₆ -alkenyl, 1-heptenyl, 2-heptenyl, 3 -Heptenyl, 1-octenyl, 2-octenyl, 3-octenyl, 4-octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 4-nonenyl, 1-decenyl, 2 -decenyl, 3-decenyl, 4-decenyl, 5-decenyl and positional isomers thereof. Examples of C ₂ -C ₂₀ -alkenyl in the strict sense (only one CC double bond) are, in addition to the examples mentioned for C ₂ -C ₁₀ -alkenyl, 1-undecenyl, 2-undecenyl, 3 -undecenyl, 4-undecenyl, 5-undecenyl, 1-dodecenyl, 2-dodecenyl, 3-dodecenyl, 4-dodecenyl, 5-dodecenyl, 6-dodecenyl, 1-tridecenyl, 2-Tridecenyl, 3-Tridecenyl, 4-Tridecenyl, 5-Tridecenyl, 6-Tridecenyl, 1-tetradecenyl, 2-tetradecenyl, 3-tetradecenyl, 4- Tetradecenyl, 5-tetradecenyl, 6-tetradecenyl, 7-tetradecenyl, 1-pentadecenyl, 2-pentadecenyl, 3-pentadecenyl, 4-pentadecenyl, 5-pentadecenyl Cenyl, 6-pentadecenyl, 7-pentadecenyl, 1-hexadecenyl, 2-hexadecenyl, 3-hexadecenyl, 4-hexadecenyl, 5-hexadecenyl, 6-hexadecenyl, 7-Hexadecenyl, 8-hexadecenyl, 1-heptadecenyl, 2-heptadecenyl, 3-heptadecenyl, 4-heptadecenyl, 5-heptadecenyl, 6-heptadecenyl, 7- Heptadecenyl, 8-heptadecenyl, 1-octadecenyl, 2-octadecenyl, 3-octadecenyl, 4-octadecenyl, 5-octadecenyl, 6-octadecenyl, 7-octade Cenyl, 8-octadecenyl, 9-octadecenyl, 1-nonadecenyl, 2-nonadecenyl, 3-nonadecenyl, 4-nonadecenyl, 5-nonadecenyl, 6-nonadecenyl, 7-nonadecenyl, 8-nonadecenyl, 9-nonadecenyl, 1-eicosadecenyl, 2-eicosadecenyl, 3-eicosadecenyl, 4-eicosadecenyl, 5-eicosadecenyl, 6- eicosadecenyl, 7-eicosadecenyl, 8-eicosadecenyl, 9-eicosadecenyl, and positional isomers thereof.

If a terminal CC double bond is present in the terminal position, ie the radical contains a C=CH ₂ group, then the alkenyl group is also termed a vinyl group.

Examples of alkapolyenyl groups are buta-1,3-dien-1-yl, buta-1,3-dien-2-yl, penta-1,3-dien-1-yl, penta-1,3- Dien-2-yl, penta-1,3-dien-3-yl, penta-1,3-dien-4-yl, penta-1,3-dien-5-yl, penta-1,4-dien- 1-yl, penta-1,4-dien-2-yl, penta-1,4-dien-3-yl, and the like.

As used herein, the term “alkynyl” generally has 2 to 40 (“C ₂ -C ₄₀ -alkynyl”) carbon atoms, preferably 2 to 30 (“C ₂ -C ₃₀ -alkynyl”) ), more preferably 2 to 20 ("C ₂ -C ₂₀ -alkynyl") carbon atoms, in particular 2 to 10 ("C ₂ -C ₁₀ -alkynyl") carbon atoms, specifically having 2 to 6 (“C ₂ -C ₆ -alkynyl”) or 2 to 4 (“C ₂ -C ₄ -alkynyl”) carbon atoms, and 1 triple bond at any position Denotes a straight-chain or branched aliphatic hydrocarbon radical. Examples of C ₂ -C ₃ -alkynyl are ethynyl, 1-propynyl or 2-propynyl. Examples of C ₂ -C ₄ -alkynyl are ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl and the like. Examples of C ₂ -C ₆ -alkynyl are ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1- Pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1 -Butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1 -Methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1- Pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-buty nyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3- butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl, and the like.

The term "cycloalkyl", when not specified as polycyclic, refers to ring members generally from 3 to 40 ("C ₃ -C ₄₀ -cycloalkyl"), preferably from 3 to 20 ("C ₃ - C ₂₀ -cycloalkyl”), in particular 3 to 10 (“C ₃ -C ₁₀ -cycloalkyl”), specifically 3 to 8 (“C ₃ -C ₈ -cycloalkyl”) or more specifically 3 to having 6 (“C ₃ -C ₆ -cycloalkyl”) carbon atoms (and of course no heteroatoms); That is, it refers to a monocyclic saturated hydrocarbon radical in which all ring members are carbon atoms. Examples of cycloalkyl having 3 to 4 carbon atoms include cyclopropyl and cyclobutyl. Examples of cycloalkyl having 3 to 5 carbon atoms include cyclopropyl, cyclobutyl and cyclopentyl. Examples of cycloalkyl having 3 to 6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Examples of cycloalkyl having 3 to 8 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of cycloalkyl having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl.

The term “polycyclic cycloalkyl” refers to ring members generally from 4 to 40 (“polycyclic C ₄ -C ₄₀ -cycloalkyl”), preferably from 4 to 20 (“polycyclic C ₄ -C ₂₀ -cycloalkyl”). alkyl"), especially having from 6 to 20 ("polycyclic C ₆ -C ₄₀ -cycloalkyl") carbon atoms (and of course no heteroatoms); That is, it refers to a non- or polycyclic saturated hydrocarbon radical in which all ring members are carbon atoms. The non- and polycyclic radicals may be fused, bridged or spiro-linked rings. Examples of bicyclic condensed saturated radicals having 6 to 10 carbon atoms are bicyclo[3.1.0]hexyl, bicyclo[3.2.0]heptyl, bicyclo[3.3.0]octyl (1,2,3, 3a,4,5,6,6a-octahydropentalenyl), bicyclo[4.2.0]octyl, bicyclo[4.3.0]nonyl (2,3,3a,4,5,6,7,7a- octahydro-1H-indene), bicyclo[4.4.0]decyl (decalinyl), and the like. Examples of bridged bicyclic condensed saturated radicals having 7 to 10 carbon atoms are bicyclo[2.2.1]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.2]octyl, bicyclo[3.2 .1] octyl and the like. Examples of bicyclic spiro-bonded saturated radicals are spiro[2.2]pentyl, spiro[2.4]heptyl, spiro[4.4]nonyl, spiro[4.5]decyl, spiro[5.5]undecyl, and the like. Examples of saturated polycyclic radicals are 2,3,4,4a,4b,5,6,7,8,8a,9,9a-dodecahydro-1H-fluorenyl, 1,2,3,4,4a ,5,6,7,8,8a,9,9a,10,10a-tetradecahydroanthracenyl, 1,2,3,4,4a,4b,5,6,7,8,8a,9,10 ,10a-tetradecahydrophenanthrenyl, 2,3,3a,4,5,6,6a,7,8,9,9a,9b-dodecahydro-1H-phenalenyl, adamantyl, and the like. .

The term "cycloalkenyl", when not specified as polycyclic, refers to ring members generally from 3 to 40 ("C ₃ -C ₄₀ -cycloalkenyl"), preferably from 3 to 20 ("C ₃ -C ₂₀ -cycloalkenyl"), in particular 3 to 10 ("C ₃ -C ₁₀ -cycloalkenyl"), specifically 3 to 8 ("C ₃ -C ₈ -cycloalkenyl") or more specifically 5 to 7 (“C ₅ -C ₇ -cycloalkenyl”) carbon atoms (and of course no heteroatoms); That is, all ring members are carbon atoms; Denotes a monocyclic partially unsaturated non-aromatic hydrocarbon radical having one or more non-consecutive, preferably one CC double bonds in the ring. Examples of C ₅ -C ₆ -cycloalkenyl include cyclopent-1-en-1-yl, cyclopent-1-en-3-yl, cyclopent-1-en-4-yl, cyclopenta-1, 3-dien-1-yl, cyclopenta-1,3-dien-2-yl, cyclopenta-1,3-dien-5-yl, cyclohex-1-en-1-yl, cyclohex-1-yl En-3-yl, cyclohex-1-en-4-yl, cyclohexa-1,3-dien-1-yl, cyclohexa-1,3-dien-2-yl, cyclohexa-1,3- dien-5-yl, cyclohexa-1,4-dien-1-yl and cyclohexa-1,4-dien-3-yl. Examples of C ₅ -C ₇ -cycloalkenyl are, in addition to those mentioned above for C ₅ -C ₆ -cycloalkenyl, cyclohept-1-en-1-yl, cyclohept-1-en-3 -yl, cyclohept-1-en-4-yl, cyclohept-1-en-5-yl, cyclohepta-1,3-dien-1-yl, cyclohepta-1,3-dien-2-yl , cyclohepta-1,3-dien-5-yl, cyclohepta-1,3-dien-6-yl, cyclohepta-1,4-dien-1-yl, cyclohepta-1,4-dien-2 -yl, cyclohepta-1,4-dien-3-yl and cyclohepta-1,4-dien-6-yl. Examples of C ₃ -C ₈ -cycloalkenyl are, in addition to those mentioned above for C ₅ -C ₇ -cycloalkenyl, cycloprop-1-en-1-yl, cycloprop-1-ene -3-yl, cyclobut-1-en-1-yl, cyclobut-1-en-3-yl, cyclooct-1-en-1-yl, cyclooct-1-en-3-yl, cyclo Oct-1-en-4-yl, cyclooct-1-en-5-yl, cycloocta-1,3-dien-1-yl, cycloocta-1,3-dien-2-yl, cycloocta- 1,3-dien-5-yl, cycloocta-1,3-dien-6-yl, cycloocta-1,4-dien-1-yl, cycloocta-1,4-dien-2-yl, cyclo Octa-1,4-dien-3-yl, cycloocta-1,4-dien-6-yl, cycloocta-1,4-dien-7-yl, cycloocta-1,5-dien-1-yl and cycloocta-1,5-dien-3-yl.

The term “polycyclic cycloalkenyl” refers to ring members generally from 4 to 40 (“polycyclic C ₄ -C ₄₀ -cycloalkenyl”), preferably from 4 to 20 (“polycyclic C ₄ -C ₂₀ ”). -cycloalkenyl"), in particular 6 to 20 ("polycyclic C ₆ -C ₄₀ -cycloalkenyl") carbon atoms (and of course no heteroatoms); That is, all ring members are carbon atoms; A non- or polycyclic unsaturated hydrocarbon radical having at least one CC double and/or triple bond, wherein the ring is not fully aromatic. The non- and polycyclic radicals may be fused, bridged or spiro-linked rings. Examples of bicyclic condensed unsaturated radicals are 1,2,3,4,4a,5,8,8a-octahydronaphthalenyl, 1,2,3,4,4a,5,6,8a-octahydronaph Talenyl, 1,2,3,4,4a,5,6,7-octahydronaphthalenyl, 1,2,3,4,5,6,7,8-octahydronaphthalenyl, 1,2 ,3,4,5,8-hexahydronaphthalenyl, 1,4,4a,5,8,8a-hexahydronaphthalenyl, indanyl, indenyl, hexahydroindenyl such as 2,3,3a ,4,7,7a-hexahydro-1H-indenyl or 2,3,3a,4,5,7a-hexahydro-1H-indenyl, tetrahydroindenyl such as 2,3,3a,7a-tetra hydro-1H-indenyl or 2,3,4,7-tetrahydro-1H-indenyl and the like. Examples of tricyclic condensed unsaturated radicals are fluorenyl, dihydrofluorenyl, tetrahydrofluorenyl, hexahydrofluorenyl and decahydrofluorenyl.

"Alkoxy" refers to an alkyl group, as defined above, attached through an oxygen atom to the remainder of the molecule; A C ₁ -C ₃₀ -alkyl group (“C ₁ -C ₃₀ -alkoxy”), preferably a C ₁ -C ₂₀ -alkyl group (“C ₁ -C”), attached via an oxygen atom to the rest of the molecule. ₂₀ -alkoxy"), in particular a C ₁ -C ₁₂ -alkyl group ("C ₁ -C ₁₂ -alkoxy"), in particular a C ₁ -C ₆ -alkyl group ("C ₁ -C ₆ -alkoxy") or C ₁ -C ₄ -alkyl group (“C ₁ -C ₄ -alkoxy”). “C ₁ -C ₂ -alkoxy” is a C ₁ -C ₂ -alkyl group, as defined above, attached through an oxygen atom. “C ₁ -C ₃ -alkoxy” is a C ₁ -C ₃ -alkyl group, as defined above, attached through an oxygen atom. C ₁ -C ₂ -alkoxy is methoxy or ethoxy. C ₁ -C ₃ -alkoxy is additionally, for example, n-propoxy and 1-methylethoxy (isopropoxy). C ₁ -C ₄ -alkoxy can additionally be, for example, butoxy, 1-methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy) or 1,1-dimethylethoxy (tert-butoxy) toxy). C ₁ -C ₆ -alkoxy is additionally, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy , 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-Dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethyl part oxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy. C ₁ -C ₈ -alkoxy is additionally, for example, heptyloxy, octyloxy, 2-ethylhexyloxy and positional isomers thereof. C ₁ -C ₁₂ -alkoxy is additionally, for example, nonyloxy, decyloxy, undecyloxy, dodecyloxy and positional isomers thereof.

The substituent “oxo” is one in which a CH ₂ group is replaced by a C(=O) group.

"Aryl" is a mono-, bi- or polycyclic carbocyclic (ie, having no heteroatoms as ring members) aromatic radicals. One example of a monocyclic aromatic radical is phenyl. In a bicyclic aryl ring, two aromatic rings are condensed, ie they share two neighboring C atoms as ring members. One example of a bicyclic aromatic radical is naphthyl. In polycyclic aryl rings, three or more rings are condensed. Examples of polycyclic aryl radicals are phenanthrenyl, anthracenyl, tetracenyl, 1H-benzo[a]phenalenyl, pyrenyl and the like. However, "aryl" in the context of the present invention means that not all rings are aromatic, however, as long as at least one ring is aromatic; It also encompasses non- or polycyclic radicals, especially when the reactive site is present on the aromatic ring (or on the functional group attached thereto). Examples thereof include indanyl, indenyl, tetralinyl, 6,7,8,9-tetrahydro-5H-benzo[7]anulenyl, fluorenyl, 9,10-dihydroanthracenyl, 9,10- dihydrophenanthrenyl, 1H-benzo[a]phenalenyl, etc., and also ring systems in which not all rings are condensed, but are, for example, spiro-linked or bridged, such as benzonorbornyl. In particular, an aryl group has as ring members 6 to 40, in particular 6 to 30, more particularly 6 to 20, in particular 6 to 10 carbon atoms.

A ring called a heterocyclic ring or heterocyclyl or heteroaromatic ring or heteroaryl or hetaryl contains as ring member at least one heteroatom, ie an atom different from carbon. In the context of the present invention, these heteroatoms are N, O and S, where N and S may also exist as heteroatom groups, ie as NO, SO or SO ₂ . Thus, in the context of the present invention, a ring named heterocyclic ring or heterocyclyl or heteroaromatic ring or heteroaryl or hetaryl is selected from the group consisting of N, O, S, NO, SO and SO ₂ as ring members. contains one or more selected heteroatoms and/or groups of heteroatoms.

In the context of the present invention, a heterocyclic ring or heterocyclyl is one or more, in particular 1, 2, 3 or 4, independently selected from the group consisting of N, O, S, NO, SO and SO ₂ as ring members. is a saturated, partially unsaturated or maximally unsaturated (including aromatic) heteromono-, bi- or polycyclic ring containing a heteroatom or group of heteroatoms (if the ring is aromatic it is also called a heteroaromatic ring or heteroaryl or hetaryl) ).

The unsaturated ring contains at least one CC and/or CN and/or NN double bond(s). A maximally unsaturated ring contains as many conjugated CC and/or CN and/or NN double bonds as the ring size allows. A maximally unsaturated 5- or 6-membered heteromonocyclic ring is generally aromatic. Exceptions are maximally unsaturated 6-membered rings which are not aromatic and contain O, S, SO and/or SO ₂ as ring members, such as pyran and thiopyran. A partially unsaturated ring contains fewer than the maximum number of CC and/or CN and/or NN double bond(s) allowed by the ring size.

The heterocyclic ring may be attached to the remainder of the molecule through a carbon ring member or through a nitrogen ring member. Naturally, the heterocyclic ring contains at least one carbon ring atom. If a ring contains more than one O ring atom, they are not contiguous. Heterocyclic rings are in particular 3- to 40-membered, especially 3- to 30-membered, more particularly 3- to 20-membered, in particular 3- to 12-membered or 3- to 11-membered.

Heteromonocyclic rings are in particular 3- to 8-membered. Examples of 3-, 4-, 5-, 6-, 7- or 8-membered saturated heteromonocyclic rings include: oxiran-2-yl, thiiran-2-yl, aziridin-1 -yl, aziridin-2-yl, oxetan-2-yl, oxetan-3-yl, thietan-2-yl, thietan-3-yl, 1-oxothietan-2-yl, 1- Oxothietan-3-yl, 1,1-dioxothietan-2-yl, 1,1-dioxothietan-3-yl, azetidin-1-yl, azetidin-2-yl, azetidine -3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, 1-oxotetrahydrothien-2-yl, 1, 1-dioxotetrahydrothien-2-yl, 1-oxotetrahydrothien-3-yl, 1,1-dioxotetrahydrothien-3-yl, pyrrolidin-1-yl, pyrrolidin-2 -yl, pyrrolidin-3-yl, pyrazolidin-1-yl, pyrazolidin-3-yl, pyrazolidin-4-yl, pyrazolidin-5-yl, imidazolidin-1- Yl, imidazolidin-2-yl, imidazolidin-4-yl, oxazolidin-2-yl, oxazolidin-3-yl, oxazolidin-4-yl, oxazolidin-5- Yl, isoxazolidin-2-yl, isoxazolidin-3-yl, isoxazolidin-4-yl, isoxazolidin-5-yl, thiazolidin-2-yl, thiazolidin- 3-yl, thiazolidin-4-yl, thiazolidin-5-yl, isothiazolidin-2-yl, isothiazolidin-3-yl, isothiazolidin-4-yl, isothiazoli Din-5-yl, 1,2,4-oxadiazolidin-2-yl, 1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-4-yl , 1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-2-yl, 1,2,4-thiadiazolidin-3-yl, 1,2, 4-thiadiazolidin-4-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-1-yl, 1,2,4-triazolidine- 3-yl, 1,2,4-triazolidin-4-yl, 1,3,4-oxadiazolidin-2-yl, 1,3,4-oxadiazolidin-3-yl, 1, 3,4-thiadiazolidin-2-yl, 1,3,4-thiadiazolidin-3-yl, 1,3,4-triazolidin-1-yl, 1,3,4-triazoli Din-2-yl, 1,3,4-triazolidin-3-yl, tetrahydropyran-2-yl, te Trihydropyran-3-yl, tetrahydropyran-4-yl, 1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 1 ,4-dioxan-2-yl, piperidin-1-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, hexahydropyridazin-1-yl , hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, hexahydropyrimidin-1-yl, hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl, hexahydropyrimidine -5-yl, piperazin-1-yl, piperazin-2-yl, 1,3,5-hexahydrotriazin-1-yl, 1,3,5-hexahydrotriazin-2-yl, 1 ,2,4-hexahydrotriazin-1-yl, 1,2,4-hexahydrotriazin-2-yl, 1,2,4-hexahydrotriazin-3-yl, 1,2,4- Hexahydrotriazin-4-yl, 1,2,4-hexahydrotriazin-5-yl, 1,2,4-hexahydrotriazin-6-yl, morpholin-2-yl, morpholine-3 -yl, morpholin-4-yl, thiomorpholin-2-yl, thiomorpholin-3-yl, thiomorpholin-4-yl, 1-oxothiomorpholin-2-yl, 1-oxothiomorph Paulin-3-yl, 1-oxothiomorpholin-4-yl, 1,1-dioxothiomorpholin-2-yl, 1,1-dioxothiomorpholin-3-yl, 1,1-di Oxothiomorpholin-4-yl, azepan-1-, -2-, -3- or -4-yl, oxepan-2-, -3-, -4- or-5-yl, hexahydro- 1,3-diazepinyl, hexahydro-1,4-diazepinyl, hexahydro-1,3-oxazepinyl, hexahydro-1,4-oxazepinyl, hexahydro-1,3-dioxepinyl nyl, hexahydro-1,4-dioxepinyl, oxokane, thiocane, azocanyl, [1,3]diazocanyl, [1,4]diazocanyl, [1,5]diazocanyl, [1,5]oxazocanyl and the like.

Examples of 3-, 4-, 5-, 6-, 7- or 8-membered partially unsaturated heteromonocyclic rings include: 2,3-dihydrofuran-2-yl, 2,3-di Hydrofuran-3-yl, 2,4-dihydrofuran-2-yl, 2,4-dihydrofuran-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien -3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyr Rollin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazoline -4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazoline -5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazoline -4-yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-di Hydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3 -dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3 ,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl , 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4 -yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazole -4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydro Oxazol-4-yl, 2-, 3-, 4-, 5- or 6-di- or tetrahydropyridinyl, 3-di- or tetrahydropyridazinyl, 4-di- or tetrahydropyridazinyl , 2-di- or tetrahydropyrimidinyl, 4-di- or tetrahydropyrimi dinyl, 5-di- or tetrahydropyrimidinyl, di- or tetrahydropyrazinyl, 1,3,5-di- or tetrahydrotriazin-2-yl, 1,2,4-di- or tetrahydro Triazin-3-yl, 2,3,4,5-tetrahydro[1H]azepin-1-, -2-, -3-, -4-, -5-, -6- or -7-yl , 3,4,5,6-tetrahydro [2H] azepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7-tetra Hydro[1H]azepine-1-, -2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7-tetrahydro[1H]azepine -1-, -2-, -3-, -4-, -5-, -6- or -7-yl, tetrahydrooxepinyl such as 2,3,4,5-tetrahydro[1H]ox Sepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro[1H]oxepin-2-, -3-, - 4-, -5-, -6- or -7-yl, 2,3,6,7-tetrahydro[1H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, tetrahydro-1,3-diazepinyl, tetrahydro-1,4-diazepinyl, tetrahydro-1,3-oxazepinyl, tetrahydro-1,4-oxazepinyl, Tetrahydro-1,3-dioxepinyl, tetrahydro-1,4-dioxepinyl, 1,2,3,4,5,6-hexahydroazosine, 2,3,4,5,6,7 - Hexahydroazosine, 1,2,3,4,5,8-hexahydroazosine, 1,2,3,4,7,8-hexahydroazosine, 1,2,3,4,5, 6-hexahydro-[1,5]diazosine, 1,2,3,4,7,8-hexahydro-[1,5]diazosine and the like.

Examples of 3-, 4-, 5-, 6-, 7- or 8-membered maximally unsaturated (but not aromatic) heteromonocyclic rings are pyran-2-yl, pyran-3-yl, pyran-4- Yl, thiopyran-2-yl, thiopyran-3-yl, thiopyran-4-yl, 1-oxothiopyran-2-yl, 1-oxothiopyran-3-yl, 1-oxothiopyran-4 -yl, 1,1-dioxothiopyran-2-yl, 1,1-dioxothiopyran-3-yl, 1,1-dioxothiopyran-4-yl, 2H-oxazin-2-yl , 2H-oxazin-3-yl, 2H-oxazin-4-yl, 2H-oxazin-5-yl, 2H-oxazin-6-yl, 4H-oxazin-3-yl, 4H-oxazin -4-yl, 4H-oxazin-5-yl, 4H-oxazin-6-yl, 6H-oxazin-3-yl, 6H-oxazin-4-yl, 7H-oxazin-5-yl, 8H-oxazin-6-yl, 2H-1,3-oxazin-2-yl, 2H-1,3-oxazin-4-yl, 2H-1,3-oxazin-5-yl, 2H- 1,3-oxazin-6-yl, 4H-1,3-oxazin-2-yl, 4H-1,3-oxazin-4-yl, 4H-1,3-oxazin-5-yl, 4H-1,3-oxazin-6-yl, 6H-1,3-oxazin-2-yl, 6H-1,3-oxazin-4-yl, 6H-1,3-oxazin-5- Yl, 6H-1,3-oxazin-6-yl, 2H-1,4-oxazin-2-yl, 2H-1,4-oxazin-3-yl, 2H-1,4-oxazin- 5-yl, 2H-1,4-oxazin-6-yl, 4H-1,4-oxazin-2-yl, 4H-1,4-oxazin-3-yl, 4H-1,4-ox Photo-4-yl, 4H-1,4-oxazin-5-yl, 4H-1,4-oxazin-6-yl, 6H-1,4-oxazin-2-yl, 6H-1,4 -oxazin-3-yl, 6H-1,4-oxazin-5-yl, 6H-1,4-oxazin-6-yl, 1,4-dioxin-2-yl, 1,4-oxa Thiin-2-yl, 1H-azepine, 1H-[1,3]-diazepine, 1H-[1,4]-diazepine, [1,3]diazosine, [1,5]diazosine, [1,5]diazosin and the like.

The heteroaromatic monocyclic ring is in particular 5- or 6-membered. Examples of 5- or 6-membered monocyclic heteroaromatic rings are 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1- Pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-oxazolyl, 4-oxa Jolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothia Zolyl, 5-isothiazolyl, 1,3,4-triazol-1-yl, 1,3,4-triazol-2-yl, 1,3,4-triazol-3-yl, 1,2 ,3-triazol-1-yl, 1,2,3-triazol-2-yl, 1,2,3-triazol-4-yl, 1,2,5-oxadiazol-3-yl, 1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,2,5-thiadia Zol-3-yl, 1,2,3-thiadiazol-4-yl, 1,2,3-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 2- Pyridinyl, 3-pyridinyl, 4-pyridinyl, 1-oxopyridin-2-yl, 1-oxopyridin-3-yl, 1-oxopyridin-4-yl, 3-pyridazinyl, 4-pyrida Zinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl , 1,2,4-triazin-5-yl, 1,2,3,4-tetrazin-1-yl, 1,2,3,4-tetrazin-2-yl, 1,2,3, 4-tetrazin-5-yl and the like.

A “heterobicyclic ring” or “heterobicyclyl” contains two rings having at least one ring atom in common. At least one of the two rings contains a heteroatom or group of heteroatoms selected from the group consisting of N, O, S, NO, SO and SO ₂ as ring members. The term refers to fused (fused) ring systems in which two rings have two neighboring ring atoms in common, as well as spiro systems in which the rings have only one ring atom in common, and at least in common. bridging systems having three ring atoms. In the context of the present invention, heterobicyclic rings include fully aromatic bicyclic ring systems; They are also termed heteroaromatic bicyclic rings or bicyclic heta(teroaryl) or heterobiaryl. The heterobicyclic ring is preferably 7-, 8-, 9-, 10- or 11-membered. The heteroaromatic bicyclic ring is preferably 9-, 10- or 11-membered. Fully heteroaromatic heterobicyclic rings are 9- or 10-membered.

Examples of fusion systems:

7-, 8-, 9-, 10 containing 1, 2 or 3 (or 4) heteroatoms or groups of heteroatoms selected from the group consisting of N, O, S, NO, SO and SO ₂ as ring members - or an example of an 11-membered saturated heterobicyclic ring is:

7-, 8-, 9-, 10 containing 1, 2 or 3 (or 4) heteroatoms or groups of heteroatoms selected from the group consisting of N, O, S, NO, SO and SO ₂ as ring members Examples of -or 11-membered partially unsaturated heterobicyclic rings are:

7-, 8-, 9-, 10 containing 1, 2 or 3 (or 4) heteroatoms or groups of heteroatoms selected from the group consisting of N, O, S, NO, SO and SO ₂ as ring members - or 11-membered maximally unsaturated (but not fully heteroaromatic) heterobicyclic rings are:

9- or 10-membered maximally unsaturated, fully unsaturated, containing 1, 2 or 3 (or 4) heteroatoms or groups of heteroatoms selected from the group consisting of N, O, S, NO, SO and SO ₂ as ring members Examples of heteroaromatic heterobicyclic rings are:

spiro-bonded 7-, 8-, containing 1, 2 or 3 (or 4) heteroatoms or groups of heteroatoms selected from the group consisting of N, O, S, NO, SO and SO ₂ as ring members; Examples of 9-, 10- or 11-membered heterobicyclic rings are:

Bridged 7-, 8-, 9- containing 1, 2 or 3 (or 4) heteroatoms or groups of heteroatoms selected from the group consisting of N, O, S, NO, SO and SO ₂ as ring members , examples of 10- or 11-membered heterobicyclic rings are:

Others of the same kind.

In the above structures, # represents the point of attachment with the rest of the molecule. The point of attachment is not limited to the ring to which it is presented, but may be on either of the two rings and may be on a carbon or nitrogen ring atom. If the ring bears one or more substituents, they may be attached to carbon and/or nitrogen ring atoms.

A polycyclic heterocyclic ring (polyheterocyclyl) contains three or more rings, each having at least one ring atom in common with at least one of the other rings of the polycyclic system. The rings may be fused, spiro-linked or bridged; Mixed systems are also possible (eg one ring is spiro-bonded to a condensed system, or a crosslinked system is condensed with another ring). wholly aromatic rings are not encompassed by polycyclic heterocyclic rings (polyheterocyclyl); They are termed polycyclic heteroaromatic rings or heteropolyaryls.

Aryloxy, heterocyclyloxy and heteroaryloxy (also expressed as O-aryl, O-heterocyclyl and O-heteroaryl) are aryl as defined above, each bound to the remainder of the molecule through an oxygen atom. , heterocyclyl and heteroaryl. Examples thereof are phenoxy or pyridyloxy.

Aryl and heterocyclic rings may be unsubstituted or may bear one or more substituents. Suitable substituents are, for example, linear or branched C ₁ -C ₁₈ -alkyl, C ₂ -C ₁₀ -alkenyl or halogen, in particular fluorine.

Examples of natural or synthetic saturated fatty acids having 2 to 41 carbon atoms are acetic acid (2 C atoms in total), propionic acid (3 C atoms in total), butyric acid (4 C atoms in total), isobutyric acid (4 C), Valeric acid (5 C), caproic acid (6 C), enantic acid (7 C), caprylic acid (8 C), 2-ethylhexanoic acid, pelargonic acid (9 C), neononanoic acid (9 C); mixture of branched isomers of n-nonanoic acid), capric acid (10 C), 3-propylheptanoic acid (10 C), neodecanoic acid (10 C; mixture of branched isomers of n-decanoic acid), unde cananoic acid (11 C), lauric acid (12 C), tridecanoic acid (13 C), myristic acid (14 C), pentadecanoic acid (15 C), palmitic acid (16 C), margaric acid ( 17 C), stearic acid (18 C), nonadecanoic acid (19 C), arachidic acid (20 C), heneicosylic acid (21 C) and behenic acid (22 C). Examples of monounsaturated fatty acids include myristoleic acid (14 C), palmitoleic acid (16 C), oleic acid (18 C), elaidic acid (18 C), gandoleic acid (20 C); gondoic acid (20 C), cetoleic acid (22 C) and erucic acid (22 C). Examples of polyunsaturated fatty acids include linoleic acid (18 C), α-linoleic acid (18 C), γ-linoleic acid (18 C), α-eleostearic acid (18 C), β-eleostearic acid (18 C), Stearidonic acid (18 C), arachidonic acid (20 C), docosadienoic acid (22 C), docosatetraenoic acid (22 C), docosapentaenoic acid (22 C) and docosahexaenoic acid ( 22 C).

"(meth)acrylate" is intended to encompass acrylates and methacrylates. "Poly(meth)acrylate" refers to polyacrylates, polymethacrylates or copolymers of acrylates and methacrylates.

In the context of the present invention, unless expressly specified otherwise, "acrylate" and "methacrylate" refer to acrylic acid or esters of methacrylic acid (and not salts thereof). This, of course, also applies to its polymers.

embodiment of the present invention

The statements made below with respect to preferred definitions of the variables and other reaction conditions are valid on their own as well as preferably in combination with one another.

Embodiments of the invention (E.x)

General and preferred embodiments E.x are summarized in the non-limiting list below. Further preferred embodiments become apparent from the paragraphs following the list below.

E.1. A process for preparing a cyclic carbonate I selected from the group consisting of a compound of formula Ia, a compound of formula Ib, and mixtures thereof, comprising:

here

R ¹ is an organic radical;

A method comprising the steps of:

a) reacting propargyl alcohol of formula II with carbon dioxide:

wherein R ¹ has the same meaning as in formula Ia or Ib,

wherein the reaction is carried out in at least one organic solvent L1 or in a solvent mixture containing at least one organic solvent L1 and at least one organic solvent L2; wherein solvent L1 has a greater polarity than solvent L2, wherein solvents L1 and L2 have a miscibility gap at least at 20-30°C;

wherein the reaction is further carried out in the presence of a silver catalyst Ag1 comprising at least one bulky ligand and a carboxylate ligand,

wherein the bulky ligand is selected from the group consisting of a ligand of formula III and a ligand of formula IV:

here

D is P, As or Sb;

each R ² is independently an organic radical having 1 to 40 carbon atoms;

R ³ and R ⁴ are the same or different and are each an organic radical having 1 to 40 carbon atoms,

R ⁵ is an organic radical having 1 to 40 carbon atoms and may be different or the same as R ² present in ligand IV;

Z is a divalent bridge selected from -CR ⁷ =CR ⁸ -, -CR ⁷ =N-, -CR ⁷ R ⁹ -CR ⁸ R ¹⁰ - and -CR ⁷ R ⁹ -CR ⁸ R ¹⁰ -CR ¹¹ R ¹² - is a flag,

here

R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are independently of each other hydrogen or an organic radical having 1 to 40 carbon atoms; or

Two adjacent radicals R ⁷ and R ⁸ and/or R ¹⁰ and R ¹¹ together with the atoms connecting them have 4 to 40 carbon atoms and also as ring members the elements Si, Ge, N, P, O and S forming a monocyclic or polycyclic, substituted or unsubstituted, aliphatic or aromatic ring system which may contain at least one heteroatom selected from the group consisting of;

wherein the carboxylate ligand is according to formula (V):

here

R ⁶ is an organic radical having 1 to 40 carbon atoms;

b1) if step a) is not carried out in the presence of at least one solvent L2, adding solvent L2 to the reaction mixture obtained in step a); or

b2) if step a) is carried out in the presence of at least one solvent L2: optionally adding solvent L2 to the reaction mixture obtained in step a);

c) subjecting the reaction mixture obtained in step a), b1) or b2) to phase separation to obtain a product phase containing cyclic carbonate I and at least one solvent L1, and a silver catalyst and at least one solvent obtaining a catalyst phase containing L2; and

d), if desired, isolating the cyclic carbonate I from the product phase.

E.2. The process as defined in embodiment 1, wherein R ¹ is hydrogen, an aliphatic radical, a cycloaliphatic radical, an aromatic radical, a mixed aliphatic-cycloaliphatic radical, a mixed aliphatic-aromatic radical, a mixed cycloaliphatic-aromatic radical and a mixed aliphatic- selected from the group consisting of cycloaliphatic-aromatic radicals,

wherein the aliphatic, cycloaliphatic and/or aromatic moieties of the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic radicals are at one or more halogen atoms. may be substituted by;

wherein the aliphatic radicals, cycloaliphatic radicals and aromatic radicals have at least one of the following features (i) and/or (ii); Mixed aliphatic-cycloaliphatic radicals, mixed aliphatic-aromatic radicals, mixed cycloaliphatic-aromatic radicals and mixed aliphatic-cycloaliphatic-aromatic radicals have at least one of the following features (i), (ii) and/or (iii) How to be:

(i) the aliphatic, cycloaliphatic and/or aromatic moieties of the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic radicals include at least one ratio -adjacent groups -O-, -S-, -N(R ¹³ )-, -OC(=O)-, -C(=O)-O-, -N(R ¹³ )-C(=O)- , -C(=O)-N(R ¹³ )-, -OC(=O)-O-, -OC(=O)-N(R ¹³ )-, -N(R ¹³ )-C(=O )-O- and/or -N(R ¹³ )-C(=O)-N(R ¹³ )- are interrupted;

(ii) aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic radicals are —OH, —SH, —N(R ¹³ ) ₂ , -OC(=O)H, -C(=O)OH, -N(R ¹³ )-C(=O)H, -C(=O)-NHR ¹³ , -OC(=O)-OH, - having one or more substituents selected from the group consisting of OC(=O)-NHR ¹³ , -N(R ¹³ )-C(=O)-OH and -N(R ¹³ )-C(=O)-NHR ¹³ box;

(iii) the aliphatic, cycloaliphatic and aromatic moieties of the mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic radicals include groups -O-, -S-, -N(R ¹³ )-, -OC(=O)-, -C(=O)-O-, -N(R ¹³ )-C(=O)-, -C(=O)-N(R ¹³ )-, -OC(=O)-O-, -OC(=O)-N(R ¹³ )-, -N(R ¹³ )-C(=O)-O- or -N(R ¹³ )-C(= bonded to each other via O)-N(R ¹³ )-;

wherein each R ¹³ is independently hydrogen or C ₁ -C ₁₀ -alkyl.

E.3. The method as defined in embodiment 1, wherein the cyclic carbonate is a compound of formula I-poly:

here

X is a bond or group -C(=O)-, ^# -C(=O)-O- ^* or ^# -C(=O)-N(R ¹³ )- ^* , where ^# is the point of attachment to O and , ^* is the point of attachment to Y (or to Z if Y is a bond or to Poly if Y and Z are bonds);

Y is a bond or a divalent aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group, wherein aliphatic, cycloaliphatic, aromatic, mixed The aliphatic, cycloaliphatic and/or aromatic moieties of the aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic bridging groups may be substituted by one or more halogen atoms;

wherein the aliphatic, cycloaliphatic or aromatic bridging group may have at least one of the following features (i) and/or (ii), mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic -aromatic bridging groups may have at least one of the following features (i), (ii) and/or (iii):

(i) at least one aliphatic, cycloaliphatic and/or aromatic moiety of an aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group; Non-adjacent groups -O-, -S-, -N(R ¹³ )-, -OC(=O)-, -C(=O)-O-, -N(R ¹³ )-C(=O) -, -C(=O)-N(R ¹³ )-, -OC(=O)-O-, -OC(=O)-N(R ¹³ )-, -N(R ¹³ )-C(= interrupted by O)-O- and/or -N(R ¹³ )-C(=O)-N(R ¹³ )-;

(ii) an aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group is —OH, —SH, —N(R ¹³ ) ₂ , -OC(=O)H, -C(=O)OH, -N(R ¹³ )-C(=O)H, -C(=O)-NHR ¹³ , -OC(=O)-OH, - having one or more substituents selected from the group consisting of OC(=O)-NHR ¹³ , -N(R ¹³ )-C(=O)-OH and -N(R ¹³ )-C(=O)-NHR ¹³ box;

(iii) the aliphatic, cycloaliphatic and/or aromatic moieties of the mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group are the groups -O-, -S-, - N(R ¹³ )-, -OC(=O)-, -C(=O)-O-, -N(R ¹³ )-C(=O)-, -C(=O)-N(R ¹³ ) )-, -OC(=O)-O-, -OC(=O)-N(R ¹³ )-, -N(R ¹³ )-C(=O)-O- or -N(R ¹³ )- bonded to each other via C(=O)-N(R ¹³ )-;

wherein each R ¹³ is independently hydrogen or C ₁ -C ₁₀ -alkyl;

Z is a bond or group -C(=O)-, ^# -C(=O)-O- ^* or ^# -C(=O)-N(R ¹³ )- ^* , when X and Y are bonds is; where ^# is the point of attachment to Y (or to X if Y is a bond or to O if X and Y are bonds), ^* is the point of attachment to Poly; or

Y is a bond and X is a group -C(=O)-, ^# -C(=O)-O- ^* or ^# -C(=O)-N(R ¹³ )- ^* where ^# is the point of attachment to O ), if it is a bond; or

When Y is a divalent aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group, a bond or group -O-, -S- , -N(R ¹³ )-, -C(=O)-, ^# -OC(=O)- ^* , ^# -C(=O)-O- ^* , ^# -N(R ¹³ )-C(= O)- ^* , ^# -C(=O)-N(R ¹³ )- ^* , ^# -OC(=O)-O- ^* , ^# -OC(=O)-N(R ¹³ )- ^* , ^# -N(R ¹³ )-C(=O)-O- ^* or ^# -N(R ¹³ )-C(=O)-N(R ¹³ )- ^* , where ^# is the point of attachment to Y;

n is 1 to 1000;

Poly is a residue derived from a polymer having a number average molecular weight of 200 to 10000;

Propargyl alcohol is a compound of formula II-poly:

wherein X, Y, Z, n and Poly are as defined above.

Way.

E.4. A method as defined in embodiment 3, comprising:

X is a bond or group -C(=O)- or ^# -C(=O)-N(R ¹³ )- ^* , where ^# is the point of attachment to O and ^* is to Y (or if Y is a bond) is the point of attachment to Z or to Poly when Y and Z are bonds;

Y is a bond or a divalent aliphatic or mixed aliphatic-cycloaliphatic bridging group having 1 to 10 carbon atoms, wherein the aliphatic or mixed aliphatic-cycloaliphatic bridging group may be substituted by one or more halogen atoms;

wherein the aliphatic bridging group may have at least one of the following features (i) and/or (ii), and the mixed aliphatic-cycloaliphatic bridging group may have at least one of the following features (i), (ii) and/or (iii) can be:

(i) the aliphatic and/or cycloaliphatic moiety of an aliphatic or mixed aliphatic-cycloaliphatic bridging group includes one or more non-adjacent groups -O-, -O-C(=O)-, -C(=O)-O-, and/or are interrupted by -O-C(=O)-O-;

(ii) the aliphatic or mixed aliphatic-cycloaliphatic bridging group bears one or more substituents selected from the group consisting of -OH, -O-C(=O)H and -C(=O)OH;

(iii) the aliphatic and/or cycloaliphatic moieties of the mixed aliphatic-cycloaliphatic bridging group are the groups -O-, -O-C(=O)-, -C(=O)-O- or -O-C(=O)-O bound to each other via ;

Z is a bond or a group -C(=O)-, when X and Y are a bond; or

when Y is a bond and X is a group -C(=O)-, it is a bond; or

when Y is a divalent aliphatic or mixed aliphatic-cycloaliphatic bridging group, a bond or group ^# -OC(=O)-;

Poly is a residue derived from poly-α-olefin or poly(meth)acrylate

Way.

E.5. The method as defined in embodiment 4, wherein -XYZ- taken together is -C(=O)-, ^# -CH ₂ -CH(OH)-CH ₂ -OC(=O)- ^* or ^# -C (=O)-NH-CH ₂ CH ₂ -OC(=O)- ^* , where ^# is the point of attachment to O and ^* is the point of attachment to Poly.

E.6. The process as defined in embodiment 2, wherein the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R ¹ consists of hydrogen and C ₁ -C ₄ -alkyl bearing the group —OR ¹⁴ . selected from the group,

here

R ¹⁴ is hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₆ -alkyl bearing 1, 2 or 3 radicals R ¹⁵ ; C ₁ -C ₆ -haloalkyl bearing 1, 2 or 3 radicals R ¹⁵ ; -C(=O)R ¹⁶ , C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl having 1, 2 or 3 radicals R ¹⁷ ; from the group consisting of phenyl and 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heterocyclic rings containing 1, 2 or 3 heteroatoms selected from N, O and S as ring members. selected, wherein the phenyl and heterocyclic rings may bear one or more substituents selected from the group consisting of C ₁ -C ₄ -alkyl and C ₁ -C ₄ -alkoxy;

here

R ¹⁵ is OH, C ₁ -C ₆ -alkoxy, oxiranyl, phenyl and the group consisting of 3-, 4-, 5- or 6-membered saturated heterocyclic rings containing 1 or 2 oxygen atoms as ring members is selected from;

R ¹⁶ is selected from the group consisting of C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₁ -C ₄ -alkoxy and —NR ¹⁸ R ¹⁹ , wherein R ¹⁸ is hydrogen or C ₁ -C ₄ -alkyl, R ¹⁹ is hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkyl substituted by the group R ²⁰ , and C ₁ -C ₄ -alkyl and C ₁ -C ₄ -alkoxy with selected from the group consisting of phenyl which may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of;

here

R ²⁰ is -OR ²¹ , -N(R ¹³ )-R ²¹ , -OC(=O)-R ²¹ , -C(=O)-OR ²¹ , -N(R ¹³ )-C(=O)- R ²¹ , -C(=O)-N(R ¹³ )-R ²¹ , -OC(=O)-OR ²¹ , -OC(=O)-N(R ¹³ )-R ²¹ , -N(R ¹³ ) )-C(=O)-OR ²¹ and -N(R ¹³ )-C(=O)-N(R ¹³ )-R ²¹ , wherein R ²¹ is hydrogen, C ₁ -C ₆ -alkyl or C ₂ -C ₆ -alkenyl, wherein each R ¹³ is independently hydrogen or C ₁ -C ₁₀ -alkyl;

R ¹⁷ is -OR ²¹ , -N(R ¹³ )-R ²¹ , -OC(=O)-R ²¹ , -C(=O)-OR ²¹ , -N(R ¹³ )-C(=O)- R ²¹ , -C(=O)-N(R ¹³ )-R ²¹ , -OC(=O)-OR ²¹ , -OC(=O)-N(R ¹³ )-R ²¹ , -N(R ¹³ ) )-C(=O)-OR ²¹ and -N(R ¹³ )-C(=O)-N(R ¹³ )-R ²¹ , wherein R ²¹ is hydrogen, C ₁ -C ₆ -alkyl or C ₂ -C ₆ -alkenyl, wherein each R ¹³ is independently hydrogen or C ₁ -C ₁₀ -alkyl;

or the cyclic carbonate is a compound of formula I-bis:

here

A is an aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group,

wherein the aliphatic, cycloaliphatic and/or aromatic moieties of the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic radicals are at one or more halogen atoms. may be substituted by;

wherein the aliphatic, cycloaliphatic or aromatic bridging group has at least one of the following features (i) and/or (ii), mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic The bridging group has at least one of the following features (i), (ii) and/or (iii):

(i) at least one aliphatic, cycloaliphatic and/or aromatic moiety of an aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group; Non-adjacent groups -O-, -S-, -N(R ¹³ )-, -OC(=O)-, -C(=O)-O-, -N(R ¹³ )-C(=O) -, -C(=O)-N(R ¹³ )-, -OC(=O)-O-, -OC(=O)-N(R ¹³ )-, -N(R ¹³ )-C(= interrupted by O)-O- and/or -N(R ¹³ )-C(=O)-N(R ¹³ )-;

(ii) an aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group is —OH, —SH, —N(R ¹³ ) ₂ , -OC(=O)H, -C(=O)OH, -N(R ¹³ )-C(=O)H, -C(=O)-NHR ¹³ , -OC(=O)-OH, - having one or more substituents selected from the group consisting of OC(=O)-NHR ¹³ , -N(R ¹³ )-C(=O)-OH and -N(R ¹³ )-C(=O)-NHR ¹³ box;

(iii) the aliphatic, cycloaliphatic and/or aromatic moieties of the mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group are the groups -O-, -S-, - N(R ¹³ )-, -OC(=O)-, -C(=O)-O-, -N(R ¹³ )-C(=O)-, -C(=O)-N(R ¹³ ) )-, -OC(=O)-O-, -OC(=O)-N(R ¹³ )-, -N(R ¹³ )-C(=O)-O- or -N(R ¹³ )- bonded to each other via C(=O)-N(R ¹³ )-;

wherein each R ¹³ is independently hydrogen or C ₁ -C ₁₀ -alkyl;

Propargyl alcohol is a compound of formula II, wherein R ¹ is selected from the group consisting of hydrogen and C ₁ -C ₄ -alkyl bearing the group —OR ¹⁴ , wherein R ¹⁴ is as defined above, or Propargyl alcohol is a compound of formula II-bis:

wherein A is as defined above

Way.

E.7. The method as defined in embodiment 6, wherein the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ ,

here

R ¹⁴ is hydrogen, C ₁ -C ₄ -alkyl bearing 1, 2 or 3 radicals R ¹⁵ ; -C(=O)R ¹⁶ and C ₃ -C ₆ -cycloalkyl bearing 1, 2 or 3 radicals R ¹⁷ ;

here

R ¹⁵ is selected from the group consisting of OH, C ₁ -C ₄ -alkoxy, phenyl and a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1 or 2 oxygen atoms as ring members; ;

R ¹⁶ is selected from the group consisting of C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₁ -C ₄ -alkoxy and —NR ¹⁸ R ¹⁹ , wherein R ¹⁸ is hydrogen or C ₁ -C ₄ -alkyl, R ¹⁹ is hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkyl substituted by the group R ²⁰ , and C ₁ -C ₄ -alkyl and C ₁ -C ₄ -alkoxy with selected from the group consisting of phenyl which may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of;

here

R ²⁰ is -OR ²¹ , -N(R ¹³ )-R ²¹ , -OC(=O)-R ²¹ , -C(=O)-OR ²¹ , -N(R ¹³ )-C(=O)- R ²¹ , -C(=O)-N(R ¹³ )-R ²¹ , -OC(=O)-OR ²¹ , -OC(=O)-N(R ¹³ )-R ²¹ , -N(R ¹³ ) )-C(=O)-OR ²¹ and -N(R ¹³ )-C(=O)-N(R ¹³ )-R ²¹ , wherein R ²¹ is hydrogen, C ₁ -C ₆ -alkyl or C ₂ -C ₆ -alkenyl, wherein each R ¹³ is independently hydrogen or C ₁ -C ₁₀ -alkyl;

R ¹⁷ is -OR ²¹ , -N(R ¹³ )-R ²¹ , -OC(=O)-R ²¹ , -C(=O)-OR ²¹ , -N(R ¹³ )-C(=O)- R ²¹ , -C(=O)-N(R ¹³ )-R ²¹ , -OC(=O)-OR ²¹ , -OC(=O)-N(R ¹³ )-R ²¹ , -N(R ¹³ ) )-C(=O)-OR ²¹ and -N(R ¹³ )-C(=O)-N(R ¹³ )-R ²¹ , wherein R ²¹ is hydrogen, C ₁ -C ₆ -alkyl or C ₂ -C ₆ -alkenyl, wherein each R ¹³ is independently hydrogen or C ₁ -C ₁₀ -alkyl;

or the cyclic carbonate is a compound of formula I-bis as defined in embodiment 6,

wherein A is selected from the following bridging groups:

-CH ₂ -O-CH ₂ -1,4-phenylene-CH ₂ -O-CH ₂ -; -CH ₂ -OC(=O)-NH-1,4-toluylene-NH-C(=O)-O-CH ₂ -; -CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) ₃ -O-CH ₂ -CH(OH)-CH ₂ -O-CH ₂ -; -CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-1,4-phenylene-C(CH ₃ ) ₂ -1,4-phenylene-O-CH ₂ -CH(OH)- CH ₂ —O—CH ₂ —; and —CH ₂ —(OCH ₂ CH ₂ ) ₃ —O—CH ₂ —;

Propargyl alcohol is a compound of formula II, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is as defined above, or propargyl alcohol is A compound of formula II-bis as defined in, wherein A is as defined above

Way.

E.8. The method as defined in embodiment 7, wherein the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ ,

here

R ¹⁴ is hydrogen, C ₁ -C ₄ -alkyl bearing 1, 2 or 3 radicals R ¹⁵ ; -C(O)CH ₃ , -C(=O)H and -C(O)OCH ₃ ;

wherein R ¹⁵ is selected from the group consisting of OH and C ₁ -C ₄ -alkoxy;

or the cyclic carbonate is a compound of formula I-bis as defined in embodiment 6, wherein A is -CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-1,4-phenyl ren-C(CH ₃ ) ₂ -1,4-phenylene-O-CH ₂ -CH(OH)-CH ₂ -O-CH ₂ -;

Propargyl alcohol is a compound of formula II, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is as defined above, or propargyl alcohol is A compound of formula II-bis as defined in, wherein A is as defined above

Way.

E.9. The method as defined in embodiment 8, wherein the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ ,

here

R ¹⁴ is selected from the group consisting of hydrogen and C ₁ -C ₄ -alkyl bearing 1 or 2 radicals R ¹⁵ ;

wherein R ¹⁵ is selected from the group consisting of OH and C ₁ -C ₄ -alkoxy;

or the cyclic carbonate is a compound of formula I-bis as defined in embodiment 6, wherein A is -CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-1,4-phenyl ren-C(CH ₃ ) ₂ -1,4-phenylene-O-CH ₂ -CH(OH)-CH ₂ -O-CH ₂ -;

Propargyl alcohol is a compound of formula II, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is as defined above, or propargyl alcohol is A compound of formula II-bis as defined in, wherein A is as defined above

Way.

E.10. The method as defined in embodiment 9, wherein the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is —CH ₂ —CH(OH)—CH ₂ —OC(CH ₃ ) ₃ or —CH ₂ —CH(OH)—CH ₂ —OH; or the cyclic carbonate is a compound of formula I-bis as defined in embodiment 6, wherein A is -CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-1,4-phenyl ren-C(CH ₃ ) ₂ -1,4-phenylene-O-CH ₂ -CH(OH)-CH ₂ -O-CH ₂ -; Propargyl alcohol is a compound of formula II, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is —CH ₂ —CH(OH)—CH ₂ —OC(CH ₃ ) ) ₃ or —CH ₂ —CH(OH)—CH ₂ —OH; or propargyl alcohol is a compound of formula II-bis as defined in embodiment 6, wherein A is -CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-1,4-phenylene -C(CH ₃ ) ₂ -1,4-phenylene-O-CH ₂ -CH(OH)-CH ₂ -O-CH ₂ -.

E.11. The method as defined in embodiment 10, wherein the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is —CH ₂ —CH(OH)—CH ₂ —OC(CH ₃ ) ₃ ; or the cyclic carbonate is a compound of formula I-bis as defined in embodiment 6, wherein A is -CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-1,4-phenyl ren-C(CH ₃ ) ₂ -1,4-phenylene-O-CH ₂ -CH(OH)-CH ₂ -O-CH ₂ -; Propargyl alcohol is a compound of formula II, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is —CH ₂ —CH(OH)—CH ₂ —OC(CH ₃ ) ) is ₃ ; or propargyl alcohol is a compound of formula II-bis as defined in embodiment 6, wherein A is -CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-1,4-phenylene -C(CH ₃ ) ₂ -1,4-phenylene-O-CH ₂ -CH(OH)-CH ₂ -O-CH ₂ -.

E.12. The method as defined in embodiment 11, wherein the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is —CH ₂ —CH(OH)—CH ₂ —OC(CH ₃ ) ₃ ; Propargyl alcohol is a compound of formula II, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is —CH ₂ —CH(OH)—CH ₂ —OC(CH ₃ ) ) _three -person method.

E.13. The method as defined in embodiment 12, wherein the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R ¹ is hydrogen and propargyl alcohol is a compound of formula II, wherein R ¹ is How to be hydrogen.

E.14. The method as defined in any one of the preceding embodiments, wherein the bulky ligand is a ligand of formula III, wherein

D is P or As,

R ² is monocyclic or polycyclic C ₃ -C ₄₀ -cycloalkyl, monocyclic or polycyclic C ₃ -C ₄₀ -cycloalkenyl, C ₆ -C ₄₀ -aryl and 3- to 40-membered saturated, a cyclic radical selected from the group consisting of partially unsaturated or maximally unsaturated mono- or polycyclic heterocyclic rings, wherein the cyclic radical may be bonded to D via an oxygen atom, wherein the cyclic radical is C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, phenyl optionally substituted by 1, 2, 3, 4 substituents R ²² , naphthyl optionally substituted by 1, 2, 3, 4 substituents R ²² , ring member A monocyclic 5- or 6-membered heteroaromatic ring containing 1, 2, 3 or 4 heteroatoms selected from the group consisting of N, O and S and optionally substituted by 1, 2 or 3 substituents R ²³ as , and fused bicyclic 8- to 10 containing 1, 2, 3 or 4 heteroatoms selected from the group consisting of N, O and S as ring members and optionally substituted by 1, 2 or 3 substituents R ²³ . - may have one or more substituents selected from the group consisting of a membered heteroaromatic ring system,

here

each R ²² is independently C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, NR ²⁴ R ²⁵ wherein R ²⁴ and R ²⁵ are independently of each other hydrogen or C ₁ -C ₁₂ -alkyl; phenyl, naphthyl and monocyclic saturated, partially unsaturated or maximally unsaturated 5- or 6-membered heterocyclic containing 1, 2, 3 or 4 heteroatoms selected from the group consisting of N, O and S as ring members selected from the group consisting of rings, wherein the last three cyclic radicals are 1, 2, 3, 4 finally selected from the group consisting of halogen, C ₁ -C ₄ -alkyl and C ₁ -C ₄ -alkoxy or 5 substituents;

each R ²³ independently has one of the meanings given for R ²² ;

R ³ and R ⁴ are independently of each other C ₁ -C ₆ -alkyl, monocyclic or polycyclic C ₃ -C ₄₀ -cycloalkyl, monocyclic or polycyclic C ₃ -C ₄₀ -cycloalkenyl and C ₆ -C ₁₀ - Which is selected from the group consisting of aryl

Way.

E.15. A method as defined in embodiment 14, comprising:

D is P;

R ² is phenyl optionally substituted by 1, 2, 3, 4 substituents R ²² , ortho-biphenyl optionally substituted by 1, 2, 3, 4 substituents R ²² , 1, 2, 3, 4 naphthyl optionally substituted by substituent R ²² , ortho-binaphthyl optionally substituted by 1, 2, 3, 4 substituents R ²² , containing 1, 2 or 3 nitrogen atoms as ring member and containing 1, 2 or monocyclic 5- or 6-membered heteroaromatic optionally substituted by 3 substituents R ²³ , and containing 1, 2 or 3 or 4 nitrogen atoms as ring members, and 1, 2 or 3 substituents R ²³ is a fused bicyclic 8- to 10-membered heteroaromatic ring system optionally substituted by

here

each R ²² is independently C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, NR ²⁴ R ²⁵ , wherein R ²⁴ and R ²⁵ independently of each other are hydrogen or C ₁ -C ₁₀ -alkyl; phenyl optionally substituted by 1, 2, 3, 4 or 5 substituents selected from the group consisting of halogen, C ₁ -C ₄ -alkyl and C ₁ -C ₄ -alkoxy; and monocyclic saturated, partially unsaturated or maximally unsaturated 5- or 6-membered heterocyclic rings containing 1, 2 or 3 heteroatoms selected from the group consisting of N and O as ring members;

each R ²³ is independently phenyl optionally substituted by 1, 2, 3, 4 or 5 substituents selected from the group consisting of halogen, C ₁ -C ₄ -alkyl and C ₁ -C ₄ -alkoxy;

R ³ and R ⁴ are independently of each other selected from the group consisting of branched C ₃ -C ₆ -alkyl, monocyclic C ₃ -C ₆ -cycloalkyl, adamantyl and phenyl.

Way.

E.16. The method as defined in embodiment 15,

D is P;

R ² is phenyl substituted by NR ²⁴ R ²⁵ , wherein R ²⁴ and R ²⁵ are independently of each other hydrogen or C ₁ -C ₁₀ -alkyl; or ortho-biphenyl substituted by 1, 2, 3 or 4 substituents R ²² ,

here

each R ²² is independently selected from the group consisting of C ₁ -C ₄ -alkyl and NR ²⁴ R ²⁵ wherein R ²⁴ and R ²⁵ are independently of each other hydrogen or C ₁ -C ₁₀ -alkyl.

Way.

E.17. The method as defined in embodiment 16, wherein R ²⁴ and R ²⁵ are independently of each other C ₃ -C ₁₀ -alkyl.

E.18. The method as defined in embodiment 14, wherein the bulky ligand is selected from compounds of formulas A to W and mixtures thereof, wherein A to W are as defined below.

E.19. The method as defined in embodiment 18, wherein the bulky ligand is selected from compounds of formulas D, V and W and mixtures thereof.

E.20. The method as defined in embodiment 19, wherein the bulky ligand is a compound of formula D (XPhos).

E.21. The method as defined in any one of embodiments 1 to 13, wherein the bulky ligand is a ligand of formula IV, wherein R ² and R ⁵ are independently of each other C ₁ -C ₆ -alkyl, C ₁ -C ₆ - C ₆ -C ₁₀ -aryl optionally substituted by 1, 2, 3, 4 or 5 substituents selected from the group consisting of alkoxy and C ₃ -C ₆ -cycloalkyl, Z is -CR ⁷ =CR ⁸ - ( wherein R ⁷ and R ⁸ are independently of each other hydrogen or C ₁ -C ₆ -alkyl.

E.22. A method as defined in embodiment 21, wherein R ² and R ⁵ are 2,6-diisopropylphenyl and Z is —CH═CH—.

E.23. The method as defined in any one of the preceding embodiments, wherein R ⁶ is C ₁ - bearing a C ₁ -C ₄₀ -alkyl, C ₂ -C ₄₀ -alkenyl, C ₃ -C ₁₀ -cycloalkyl ring. C ₆ -alkyl, wherein the C ₃ -C ₁₀ -cycloalkyl ring may bear 1, 2, 3, 4 or 5 C ₁ -C ₆ -alkyl substituents; C ₁ -C ₄ -alkyl having a C ₆ -C ₁₀ -aryl ring, wherein the C ₆ -C ₁₀ -aryl ring is 1 selected from the group consisting of C ₁ -C ₆ -alkyl and C ₁ -C ₆ -alkoxy , which may have 2, 3, 4 or 5 substituents); and C ₆ -C ₁₀ -aryl which may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of C ₁ -C ₆ -alkyl and C ₁ -C ₆ -alkoxy how it is.

E.24. The method as defined in embodiment 23, wherein R ⁶ has C ₁ -C ₃₀ -alkyl, C ₆ -C ₃₀ -alkenyl and C ₃ -C ₆ -cycloalkyl rings C ₁ -C ₄ - and is selected from the group consisting of alkyl.

E.25. The method as defined in embodiment 24, wherein R ⁶ is selected from the group consisting of C ₁ -C ₂₂ -alkyl and C ₁ -C ₄ -alkyl having C ₅ -C ₆ -cycloalkyl rings. Way.

E.26. The method as defined in embodiment 25, wherein R ⁶ is selected from the group consisting of C ₁ -C ₂₀ -alkyl and C ₂ -C ₄ -alkyl having a cyclohexyl ring.

E.27. The method as defined in embodiment 26, wherein R ⁶ is selected from the group consisting of C ₈ -C ₁₈ -alkyl and C ₂ -C ₄ -alkyl having a cyclohexyl ring.

E.28. The method as defined in any one of embodiments 1-22, wherein R ⁶ is C ₂ -C ₄₀ -alkyl, C ₂ -C ₄₀ -alkenyl, C ₃ -C ₁₀ -cycloalkyl having a ring. ₁ -C ₆ -alkyl, wherein the C ₃ -C ₁₀ -cycloalkyl ring may bear 1, 2, 3, 4 or 5 C ₁ -C ₆ -alkyl substituents; C ₁ -C ₄ -alkyl having a C ₆ -C ₁₀ -aryl ring, wherein the C ₆ -C ₁₀ -aryl ring is 1 selected from the group consisting of C ₁ -C ₆ -alkyl and C ₁ -C ₆ -alkoxy , which may have 2, 3, 4 or 5 substituents); and C ₆ -C ₁₀ -aryl which may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of C ₁ -C ₆ -alkyl and C ₁ -C ₆ -alkoxy how it is.

E.29. The method as defined in embodiment 28, wherein R ⁶ has C ₆ -C ₃₀ -alkyl, C ₆ -C ₃₀ -alkenyl and C ₃ -C ₆ -cycloalkyl rings C ₁ -C ₄ - and is selected from the group consisting of alkyl.

E.30. The method as defined in embodiment 29, wherein R ⁶ is selected from the group consisting of C ₆ -C ₂₂ -alkyl and C ₁ -C ₄ -alkyl having C ₅ -C ₆ -cycloalkyl rings. Way.

E.31. The method as defined in embodiment 30, wherein R ⁶ is selected from the group consisting of C ₈ -C ₂₀ -alkyl and C ₂ -C ₄ -alkyl having a cyclohexyl ring.

E.32. The method as defined in embodiment 31, wherein R ⁶ is selected from the group consisting of C ₈ -C ₁₈ -alkyl and C ₂ -C ₄ -alkyl having a cyclohexyl ring.

E.33. A process as defined in any one of the preceding embodiments, wherein the silver catalyst Ag1 is a pre-formed catalyst or is a silver compound or silver salt containing no bulky ligand with a silver pro-catalyst and a compound of formula III, carr of formula IV formed in situ by reaction of benes or precursors of carbenes of formula IV;

wherein if the silver pro-catalyst does not contain a carboxylate ligand V, the silver pro-catalyst is also combined with the corresponding acid R ⁶ -C(=O)OH of the carboxylate ligand V or with the formula R ⁶ -C ( =O)O ^- M ⁺ (where M ⁺ is the cation equivalent) with its salt;

wherein in the case of in situ formation of the silver catalyst Ag 1, the compound of formula III, carbene of formula IV or precursor of carbene of formula IV is used in an amount of 0.2 to 1.8 mol per mol of silver present in the silver pro-catalyst that

Way.

E.34. The method as defined in embodiment 33, wherein the precursor of the carbene of formula IV is a compound of formula VI, wherein when compound VI is used, it is used together with a base:

wherein R ² , R ⁵ and Z are as defined in any one of embodiments 1, 21 or 22, and X ⁻ is an anionic equivalent.

E.35. The method as defined in any one of embodiments 33 or 34, wherein in the case of in situ formation of the silver catalyst Ag 1, the compound of formula III, carbene of formula IV or precursor of carbene of formula IV is a silver pro- The process according to claim 1, wherein the amount is used in an amount of from 0.3 to 1.5 moles per mole of silver present in the catalyst.

E.36. The method as defined in embodiment 35, wherein in the case of in situ formation of the silver catalyst Ag 1 , the compound of formula III, the carbene of formula IV or the precursor of the carbene of formula IV is the amount of silver present in the silver pro-catalyst. used in an amount of from 0.4 to 1.2 mols per mol.

E.37. The method as defined in embodiment 36, wherein, in the case of in situ formation of the silver catalyst Ag 1 , the compound of formula III, the carbene of formula IV or the precursor of the carbene of formula IV is the amount of silver present in the silver pro-catalyst. used in an amount of 0.8 to 1.2 mol per mol.

E.38. The process as defined in any one of the preceding embodiments, wherein the silver catalyst Ag1 is used in step a) in an amount of from 0.001 to 50 mol %, based on the amount of propargyl alcohol of formula (II). Way.

E.39. The process as defined in embodiment 38, wherein the silver catalyst Ag1 is used in step a) in an amount of from 0.001 to 20 mol%, based on the amount of propargyl alcohol of formula (II).

E.40. The process as defined in embodiment 39, wherein the silver catalyst Ag1 is used in step a) in an amount of from 0.005 to 10 mol %, based on the amount of propargyl alcohol of formula (II).

E.41. The process as defined in embodiment 40, wherein the silver catalyst Ag1 is used in step a) in an amount of from 0.01 to 5 mol %, based on the amount of propargyl alcohol of formula (II).

E.42. The process as defined in embodiment 41, wherein the silver catalyst Ag1 is used in step a) in an amount of from 0.5 to 3 mol-%, based on the amount of propargyl alcohol of formula (II).

E.43. The method as defined in any one of the preceding embodiments, wherein the solvent L1 is a polar aprotic solvent having a dipole moment of at least 10·10 ⁻³⁰ C·m.

E.44. The method as defined in embodiment 43, wherein the solvent L1 is a polar aprotic solvent having a dipole moment of at least 11·10 ^-30 C·m.

E.45. The process as defined in any one of the preceding embodiments, wherein the solvent L2 is a non-polar solvent having a dipole moment of at most 2·10 ⁻³⁰ C·m.

E.46. The process as defined in embodiment 45, wherein the solvent L2 is a non-polar solvent having a dipole moment of at most 1·10 ⁻³⁰ C·m.

E.47. The method as defined in embodiment 46, wherein the solvent L2 is a non-polar solvent having a dipole moment of 0 C·m.

E.48. The process as defined in any one of the preceding embodiments, wherein the solvent L1 is selected from the group consisting of amides, ureas, nitriles, sulfoxides, sulfones, ethers, esters, carbonates, nitro compounds and mixtures thereof, the solvent L2 is selected from the group consisting of alkanes, cycloalkanes and C ₁ -C ₂ -alkyl esters of C ₁₂ -C ₂₀ -fatty acids.

E.49. The method as defined in embodiment 48, wherein the solvent L1 is a polar aprotic solvent and is formamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea , N,N-dimethylimidazolinone, N,N-dimethylpropyleneurea, acetonitrile, propionitrile, benzonitrile, dimethyl sulfoxide, sulfolane, dimethyl carbonate, diethyl carbonate, ethylene carbon nate, propylene carbonate, nitromethane, nitrobenzene and mixtures thereof.

E.50. The method as defined in any one of embodiments 48 or 49, wherein the solvent L2 is a C ₅ -C ₁₅ -alkane, a C ₅ -C ₈ -cycloalkane which may bear C ₁ -C ₂ -alkyl substituents; C ₁₂ -C ₂₀ -C ₁ -C ₂ -alkyl esters of fatty acids and mixtures thereof.

E.51. The method as defined in any one of embodiments 48 to 50,

- solvent L1 is acetonitrile and solvent L2 is C ₅ -C ₁₄ -alkanes, C ₅ -C ₈ -cycloalkanes which may bear C ₁ -C ₂ -alkyl substituents, and saturated C ₁₂ -C ₂₀ fatty acids selected from the group consisting of C ₁ -C ₂ -alkyl esters; or

- solvent L1 is dimethylformamide and solvent L2 is C ₅ -C ₁₄ -alkanes, C ₅ -C ₈ -cycloalkanes which may bear C ₁ -C ₂ -alkyl substituents, and saturated C ₁₂ -C ₂₀ fatty acids which is selected from the group consisting of C ₁ -C ₂ -alkyl esters of

Way.

E.52. A method as defined in embodiment 51,

- solvent L1 is acetonitrile and solvent L2 is selected from the group consisting of C ₅ -C ₁₂ -alkanes and C ₆ -C ₈ -cycloalkanes; or

- solvent L1 is dimethylformamide and solvent L2 is selected from the group consisting of C ₅ -C ₁₂ -alkanes and C ₅ -C ₈ -cycloalkanes

Way.

E.53. The process as defined in embodiment 52, wherein solvent L1 is acetonitrile, solvent L2 is cyclohexane or decane, or solvent L1 is dimethylformamide and solvent L2 is hexane.

E.54. The process as defined in embodiment 53, wherein the solvent L1 is acetonitrile and the solvent L2 is cyclohexane or decane.

E.55. The method as defined in any one of the preceding embodiments, wherein in step a) propargyl alcohol is present in an amount of 0.1 to 25% by weight, relative to the total weight of all solvents used in step a). how to be.

E.56. The process as defined in embodiment 55, wherein in step a) propargyl alcohol is present in an amount of from 0.5 to 20% by weight relative to the total weight of all solvents used in step a).

E.57. The process as defined in embodiment 56, wherein in step a) propargyl alcohol is present in an amount of 1 to 20% by weight relative to the total weight of all solvents used in step a).

E.58. The process as defined in embodiment 57, wherein in step a) propargyl alcohol is present in an amount of from 1 to 15% by weight relative to the total weight of all solvents used in step a).

E.59. The process as defined in any one of the preceding embodiments, wherein step a) is carried out at a pressure in the range from 0.1 to 200 bar.

E.60. The process as defined in embodiment 59, wherein step a) is carried out at a pressure in the range from 1 to 100 bar.

E.61. The process as defined in embodiment 60, wherein step a) is carried out at a pressure in the range from 5 to 80 bar.

E.62. The process as defined in any one of the preceding embodiments, wherein step a) is carried out at a temperature in the range from 0 to 100°C.

E.63. The process as defined in embodiment 62, wherein step a) is carried out at a temperature in the range from 10 to 80°C.

E.64. The process as defined in embodiment 63, wherein step a) is carried out at a temperature in the range from 10 to 40°C.

E.65. The process as defined in any one of the preceding embodiments, wherein in step a) no solvent L2 is used and step b1) is carried out.

E.66. The process as defined in any one of the preceding embodiments, wherein in step c) solvent L1 and solvent L2 are present in a total weight ratio of 80:20 to 20:80.

E.67. The process as defined in embodiment 66, wherein in step c) solvent L1 and solvent L2 are present in a total weight ratio of 70:30 to 30:70.

E.68. The process as defined in embodiment 67, wherein in step c) solvent L1 and solvent L2 are present in a total weight ratio of 60:40 to 40:60.

E.69. The process as defined in any one of the preceding embodiments, wherein the product phase obtained in step c) contains more than 50% by weight of the cyclic carbonate I formed in step a) and the catalyst phase comprises more than 50% by weight of the catalyst phase. and a silver catalyst.

E.70. The process as defined in embodiment 69, wherein the product phase obtained in step c) contains more than 66.7% by weight of the cyclic carbonate I formed in step a) and the catalyst phase comprises more than 66.7% by weight of a silver catalyst containing it.

E.71. The process as defined in embodiment 70, wherein the product phase obtained in step c) contains more than 83.3% by weight of the cyclic carbonate I formed in step a) and the catalyst phase comprises more than 83.3% by weight of a silver catalyst containing it.

radical R ¹

In compounds I and II, R ¹ is an organic radical. As explained above, these radicals may be derived from individual molecules or from polymers. When R ¹ is derived from a polymer, the starting compound II generally contains more than one group -C≡C-CH ₂ OH (and naturally the final product is a cyclic carbonate group bonded via a vinylidene group). usually contains more than one). As already explained above, these groups may be attached to the polymer backbone either directly or via a linking group. By way of example only, it contains a carboxyl group or carboxyl derivative susceptible to esterification (exchange) reaction, or contains an oxiranyl ring such as is present at a glycidyl moiety, or contains a chlorohydrin moiety or an isocyanate group (-NCO ) or a polymer or monomer containing another group in the side chain capable of reacting with an alcohol group is reacted with 1,4-butynediol or another diol containing a propargyl alcohol group, so that R ¹ is a group -C≡C- in the side chain It is possible to provide (polymeric) compounds II, which are derived from polymers containing many CH ₂ OH. If the monomer is reacted with 1,4-butynediol or another diol, the polymer is of course obtained after polymerization of this monomer. In product I resulting from the reaction of the polymer with CO ₂ R ¹ is a plurality of cyclic carbonate groups bonded via an exocyclic vinylidene group (more precisely 1,3-dioxolan-2-one-4- one ring). Alternatively, the monomer may first be reacted with CO ₂ under the reaction conditions described above and below to provide a monomer containing the exo-vinylidene-bonded cyclic carbonate, which is subsequently polymerized. Alternatively, the monomer may first be reacted with CO ₂ under the reaction conditions described above and below to provide a monomer containing the exo-vinylidene-bonded cyclic carbonate, which is subsequently polymerized. By way of example only, polyacrylic acid or polymethacrylic acid or polyacrylate or polymethacrylate susceptible to transesterification is esterified with 1,4-butynediol to form a repeating unit -[CH ₂ -CH(C(=O)) OCH ₂ C≡CH ₂ OH)]- or -[CH ₂ -CCH ₃ (C(=O)OCH ₂ C≡CH ₂ OH)]-; or polyacrylates or polymethacrylates containing an NCO group in the alcohol-derived portion of the ester (eg alcohol-derived portion derived from HO-CH ₂ CH ₂ -NCO) with 1,4-butynediol reacted by an addition reaction to the repeating unit -[CH ₂ -CH(C(=O)O-CH ₂ CH ₂ -NH-C(=O)-O-CH ₂ C≡CH ₂ OH)]- or -[CH ₂ -C(CH ₃ )(C(=O)O-CH ₂ CH ₂ -NH-C(=O)-O-CH ₂ C≡CH ₂ OH)]-; Alternatively, a polyacrylate or polymethacrylate containing a glycidyl moiety or a chlorohydrin moiety may be reacted with 1,4-butynediol by an addition or substitution reaction. Alternatively, the corresponding acrylate or methacrylate monomers are first prepared by the esterification/addition/substitution reaction described above and then polymerized. As yet another alternative, the corresponding acrylate or methacrylate monomers can be grafted onto a polymer having a suitable backbone, for example onto a polyethylene or polypropylene polymer. However, polymer moieties are not limited to these few examples; It can be derived from a wide variety of polymer types, such as polymers with polyolefin backbones, poly(meth)acrylates, polyesters, polyethers, polyurethanes, polyureas, polyamides, polycarbonates, and the like.

For the avoidance of any doubt, even where R ¹ is derived from an individual molecule, the starting compound may nevertheless contain more than one group -C≡C-CH ₂ OH (and the final product as well) naturally contain more than one cyclic carbonate group bonded via a vinylidene group).

In a preferred embodiment, the cyclic carbonate is a compound Ia, a compound Ib or a mixture thereof, wherein R ¹ is hydrogen, an aliphatic radical, a cycloaliphatic radical, an aromatic radical, a mixed aliphatic-cycloaliphatic radical, a mixed aliphatic-aromatic radical, selected from the group consisting of mixed cycloaliphatic-aromatic radicals and mixed aliphatic-cycloaliphatic-aromatic radicals;

wherein the aliphatic, cycloaliphatic and/or aromatic moieties of the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic radicals are at one or more halogen atoms. may be substituted by;

wherein the aliphatic radicals, cycloaliphatic radicals and aromatic radicals have at least one of the following features (i) and/or (ii); Mixed aliphatic-cycloaliphatic radicals, mixed aliphatic-aromatic radicals, mixed cycloaliphatic-aromatic radicals and mixed aliphatic-cycloaliphatic-aromatic radicals have at least one of the following features (i), (ii) and/or (iii):

(i) the aliphatic, cycloaliphatic and/or aromatic moieties of the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic radicals include at least one ratio -adjacent groups -O-, -S-, -N(R ¹³ )-, -OC(=O)-, -C(=O)-O-, -N(R ¹³ )-C(=O)- , -C(=O)-N(R ¹³ )-, -OC(=O)-O-, -OC(=O)-N(R ¹³ )-, -N(R ¹³ )-C(=O )-O- and/or -N(R ¹³ )-C(=O)-N(R ¹³ )- are interrupted;

(ii) aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic radicals are —OH, —SH, —N(R ¹³ ) ₂ , -OC(=O)H, -C(=O)OH, -N(R ¹³ )-C(=O)H, -C(=O)-NHR ¹³ , -OC(=O)-OH, - having one or more substituents selected from the group consisting of OC(=O)-NHR ¹³ , -N(R ¹³ )-C(=O)-OH and -N(R ¹³ )-C(=O)-NHR ¹³ box;

(iii) the aliphatic, cycloaliphatic and aromatic moieties of the mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic radicals include groups -O-, -S-, -N(R ¹³ )-, -OC(=O)-, -C(=O)-O-, -N(R ¹³ )-C(=O)-, -C(=O)-N(R ¹³ )-, -OC(=O)-O-, -OC(=O)-N(R ¹³ )-, -N(R ¹³ )-C(=O)-O- or -N(R ¹³ )-C(= bonded to each other via O)-N(R ¹³ )-;

wherein each R ¹³ is independently hydrogen or C ₁ -C ₁₀ -alkyl.

In a more preferred embodiment, the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R ¹ is selected from the group consisting of hydrogen and C ₁ -C ₄ -alkyl bearing the group —OR ¹⁴ ,

here

R ¹⁴ is hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₆ -alkyl bearing 1, 2 or 3 radicals R ¹⁵ ; C ₁ -C ₆ -haloalkyl bearing 1, 2 or 3 radicals R ¹⁵ ; -C(=O)R ¹⁶ , C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl having 1, 2 or 3 radicals R ¹⁷ ; from the group consisting of phenyl and 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heterocyclic rings containing 1, 2 or 3 heteroatoms selected from N, O and S as ring members. selected, wherein the phenyl and heterocyclic rings may bear one or more substituents selected from the group consisting of C ₁ -C ₄ -alkyl and C ₁ -C ₄ -alkoxy;

here

R ¹⁵ is OH, C ₁ -C ₆ -alkoxy, oxiranyl, phenyl and the group consisting of 3-, 4-, 5- or 6-membered saturated heterocyclic rings containing 1 or 2 oxygen atoms as ring members is selected from;

R ¹⁶ is selected from the group consisting of C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₁ -C ₄ -alkoxy and —NR ¹⁸ R ¹⁹ , wherein R ¹⁸ is hydrogen or C ₁ -C ₄ -alkyl, R ¹⁹ is hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkyl substituted by the group R ²⁰ , and C ₁ -C ₄ -alkyl and C ₁ -C ₄ -alkoxy with selected from the group consisting of phenyl which may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of;

here

R ²⁰ is -OR ²¹ , -N(R ¹³ )-R ²¹ , -OC(=O)-R ²¹ , -C(=O)-OR ²¹ , -N(R ¹³ )-C(=O)- R ²¹ , -C(=O)-N(R ¹³ )-R ²¹ , -OC(=O)-OR ²¹ , -OC(=O)-N(R ¹³ )-R ²¹ , -N(R ¹³ ) )-C(=O)-OR ²¹ and -N(R ¹³ )-C(=O)-N(R ¹³ )-R ²¹ , wherein R ²¹ is hydrogen, C ₁ -C ₆ -alkyl or C ₂ -C ₆ -alkenyl, wherein each R ¹³ is independently hydrogen or C ₁ -C ₁₀ -alkyl;

R ¹⁷ is -OR ²¹ , -N(R ¹³ )-R ²¹ , -OC(=O)-R ²¹ , -C(=O)-OR ²¹ , -N(R ¹³ )-C(=O)- R ²¹ , -C(=O)-N(R ¹³ )-R ²¹ , -OC(=O)-OR ²¹ , -OC(=O)-N(R ¹³ )-R ²¹ , -N(R ¹³ ) )-C(=O)-OR ²¹ and -N(R ¹³ )-C(=O)-N(R ¹³ )-R ²¹ , wherein R ²¹ is hydrogen, C ₁ -C ₆ -alkyl or C ₂ -C ₆ -alkenyl, wherein each R ¹³ is independently as defined above (ie hydrogen or C ₁ -C ₁₀ -alkyl);

or the cyclic carbonate is a compound of formula I-bis:

here

A is an aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group,

wherein the aliphatic, cycloaliphatic and/or aromatic moieties of the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic radicals are at one or more halogen atoms. may be substituted by;

wherein the aliphatic, cycloaliphatic or aromatic bridging group has at least one of the following features (i) and/or (ii), mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic The bridging group has at least one of the following features (i), (ii) and/or (iii):

(i) at least one aliphatic, cycloaliphatic and/or aromatic moiety of an aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group; Non-adjacent groups -O-, -S-, -N(R ¹³ )-, -OC(=O)-, -C(=O)-O-, -N(R ¹³ )-C(=O) -, -C(=O)-N(R ¹³ )-, -OC(=O)-O-, -OC(=O)-N(R ¹³ )-, -N(R ¹³ )-C(= interrupted by O)-O- and/or -N(R ¹³ )-C(=O)-N(R ¹³ )-;

(ii) an aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group is —OH, —SH, —N(R ¹³ ) ₂ , -OC(=O)H, -C(=O)OH, -N(R ¹³ )-C(=O)H, -C(=O)-NHR ¹³ , -OC(=O)-OH, - having one or more substituents selected from the group consisting of OC(=O)-NHR ¹³ , -N(R ¹³ )-C(=O)-OH and -N(R ¹³ )-C(=O)-NHR ¹³ box;

(iii) the aliphatic, cycloaliphatic and/or aromatic moieties of the mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group are the groups -O-, -S-, - N(R ¹³ )-, -OC(=O)-, -C(=O)-O-, -N(R ¹³ )-C(=O)-, -C(=O)-N(R ¹³ ) )-, -OC(=O)-O-, -OC(=O)-N(R ¹³ )-, -N(R ¹³ )-C(=O)-O- or -N(R ¹³ )- bonded to each other via C(=O)-N(R ¹³ )-;

wherein each R ¹³ is independently hydrogen or C ₁ -C ₁₀ -alkyl.

Thus, propargyl alcohol is preferably a compound of formula II, wherein R ¹ is selected from the group consisting of hydrogen and C ₁ -C ₄ -alkyl bearing the group —OR ¹⁴ , wherein R ¹⁴ is a cyclic car As defined in the above preferred embodiment of the bonate, or propargyl alcohol is a compound of formula II-bis:

wherein A is as defined in the above preferred embodiment of the cyclic carbonate I-bis.

More preferably, the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ ,

here

R ¹⁴ is hydrogen, C ₁ -C ₄ -alkyl bearing 1, 2 or 3 radicals R ¹⁵ ; -C(=O)R ¹⁶ and C ₃ -C ₆ -cycloalkyl bearing 1, 2 or 3 radicals R ¹⁷ ;

here

R ¹⁵ is selected from the group consisting of OH, C ₁ -C ₄ -alkoxy, phenyl and a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1 or 2 oxygen atoms as ring members; ;

R ¹⁶ is selected from the group consisting of C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₁ -C ₄ -alkoxy and —NR ¹⁸ R ¹⁹ , wherein R ¹⁸ is hydrogen or C ₁ -C ₄ -alkyl, R ¹⁹ is hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkyl substituted by the group R ²⁰ , and C ₁ -C ₄ -alkyl and C ₁ -C ₄ -alkoxy with selected from the group consisting of phenyl which may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of;

here

R ²⁰ is -OR ²¹ , -N(R ¹³ )-R ²¹ , -OC(=O)-R ²¹ , -C(=O)-OR ²¹ , -N(R ¹³ )-C(=O)- R ²¹ , -C(=O)-N(R ¹³ )-R ²¹ , -OC(=O)-OR ²¹ , -OC(=O)-N(R ¹³ )-R ²¹ , -N(R ¹³ ) )-C(=O)-OR ²¹ and -N(R ¹³ )-C(=O)-N(R ¹³ )-R ²¹ , wherein R ²¹ is hydrogen, C ₁ -C ₆ -alkyl or C ₂ -C ₆ -alkenyl, wherein each R ¹³ is independently hydrogen or C ₁ -C ₁₀ -alkyl;

R ¹⁷ is -OR ²¹ , -N(R ¹³ )-R ²¹ , -OC(=O)-R ²¹ , -C(=O)-OR ²¹ , -N(R ¹³ )-C(=O)- R ²¹ , -C(=O)-N(R ¹³ )-R ²¹ , -OC(=O)-OR ²¹ , -OC(=O)-N(R ¹³ )-R ²¹ , -N(R ¹³ ) )-C(=O)-OR ²¹ and -N(R ¹³ )-C(=O)-N(R ¹³ )-R ²¹ , wherein R ²¹ is hydrogen, C ₁ -C ₆ -alkyl or C ₂ -C ₆ -alkenyl, wherein each R ¹³ is independently hydrogen or C ₁ -C ₁₀ -alkyl;

or the cyclic carbonate is a compound of formula I-bis as defined above,

wherein A is selected from the following bridging groups:

-CH ₂ -O-CH ₂ -1,4-phenylene-CH ₂ -O-CH ₂ -;

-CH ₂ -OC(=O)-NH-1,4-toluylene-NH-C(=O)-O-CH ₂ -;

-CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) ₃ -O-CH ₂ -CH(OH)-CH ₂ -O-CH ₂ -;

-CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-1,4-phenylene-C(CH ₃ ) ₂ -1,4-phenylene-O-CH ₂ -CH(OH)- CH ₂ —O—CH ₂ —; and

-CH ₂ -(OCH ₂ CH ₂ ) ₃ -O-CH ₂ -;

therefore,

Propargyl alcohol is more preferably a compound of formula II, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is in said more preferred embodiment of the cyclic carbonate or propargyl alcohol is a compound of formula II-bis, wherein A is as defined in the above more preferred embodiment of the cyclic carbonate.

1,4-Toluylene is a divalent group of the formula:

# represents the point of attachment (with NH in the formula above).

Even more preferably, the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ ,

here

R ¹⁴ is hydrogen, C ₁ -C ₄ -alkyl bearing 1, 2 or 3 radicals R ¹⁵ ; -C(O)CH ₃ , -C(=O)H and -C(O)OCH ₃ ;

here

R ¹⁵ is selected from the group consisting of OH and C ₁ -C ₄ -alkoxy;

or the cyclic carbonate is a compound of formula I-bis as defined above, wherein A is -CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-1,4-phenylene-C (CH ₃ ) ₂ -1,4-phenylene-O-CH ₂ -CH(OH)-CH ₂ -O-CH ₂ -;

therefore,

Propargyl alcohol is in particular a compound of formula II, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is as defined in the above specific embodiment of the cyclic carbonate. or propargyl alcohol is a compound of formula II-bis, wherein A is as defined in the particular embodiment above for cyclic carbonate.

In particular, the cyclic carbonate is a compound Ia, a compound Ib or a mixture thereof, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ ,

here

R ¹⁴ is selected from the group consisting of hydrogen and C ₁ -C ₄ -alkyl bearing 1 or 2 radicals R ¹⁵ ;

here

R ¹⁵ is selected from the group consisting of OH and C ₁ -C ₄ -alkoxy;

or the cyclic carbonate is a compound of formula I-bis as defined in embodiment 6, wherein A is -CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-1,4-phenyl ren-C(CH ₃ ) ₂ -1,4-phenylene-O-CH ₂ -CH(OH)-CH ₂ -O-CH ₂ -;

therefore,

Propargyl alcohol is a compound of formula II, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is as defined above, or propargyl alcohol is selected from the group consisting of: A compound of formula II-bis as defined in, wherein A is as defined above.

More particularly, the cyclic carbonate is compound Ia, compound Ib or mixtures thereof, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is —CH ₂ —CH(OH) —CH ₂ —OC(CH ₃ ) ₃ or —CH ₂ —CH(OH)—CH ₂ —OH; or the cyclic carbonate is a compound of formula I-bis as defined in embodiment 6, wherein A is -CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-1,4-phenyl ren-C(CH ₃ ) ₂ -1,4-phenylene-O-CH ₂ -CH(OH)-CH ₂ -O-CH ₂ -;

therefore,

Propargyl alcohol is a compound of formula II, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is —CH ₂ —CH(OH)—CH ₂ —OC(CH ₃ ) ) ₃ or —CH ₂ —CH(OH)—CH ₂ —OH; or propargyl alcohol is a compound of formula II-bis as defined in embodiment 6, wherein A is -CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-1,4-phenylene -C(CH ₃ ) ₂ -1,4-phenylene-O-CH ₂ -CH(OH)-CH ₂ -O-CH ₂ -.

In a more specific embodiment, the cyclic carbonate is compound Ia, compound Ib, or a mixture thereof, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is —CH ₂ —CH (OH)—CH ₂ —OC(CH ₃ ) ₃ ; or the cyclic carbonate is a compound of formula I-bis as defined above, wherein A is -CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-1,4-phenylene-C (CH ₃ ) ₂ -1,4-phenylene-O-CH ₂ -CH(OH)-CH ₂ -O-CH ₂ -;

Accordingly, propargyl alcohol is more particularly a compound of formula II, wherein R ¹ is selected from the group consisting of hydrogen and —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is —CH ₂ —CH(OH)—CH ₂ — OC(CH ₃ ) ₃ ; or propargyl alcohol is a compound of formula II-bis as defined above, wherein A is -CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-1,4-phenylene-C( CH ₃ ) ₂ -1,4-phenylene-O-CH ₂ -CH(OH)-CH ₂ -O-CH ₂ -.

The bridging group A has the formula:

where # is the point of attachment with the exo-vinylidene group at I-bis and the triple bond at II-bis.

Specifically, the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R ¹ is hydrogen and propargyl alcohol is a compound of formula II, wherein R ¹ is hydrogen.

In an alternative embodiment, R ¹ is derived from a polymer.

Suitable polymers include, for example, polyolefins (more precisely polymers having a polyolefin backbone), poly(meth)acrylates, polyesters, polyethers, polyurethanes, polyureas, polyamides, polycarbonates and mixtures thereof; That is, for example, a polyolefin grafted with (meth)acrylate to yield a polymer having a polyolefin backbone and poly(meth)acrylate side chains, or block copolymers having blocks derived from different polymer types, or amines of isocyanates and polymers containing in polymerized form the monomers characteristic for said polymers of different types, such as those present in polymers obtained from reaction with both alcohols and the like. In particular, the polymer is a poly(meth)acrylate, in particular a polymethacrylate.

In case R ¹ is derived from a polymer, the cyclic carbonate is preferably a compound of formula I-poly:

here

X is a bond or group -C(=O)-, ^# -C(=O)-O- ^* or ^# -C(=O)-N(R ¹³ )- ^* , where ^# is the point of attachment to O and , ^* is the point of attachment to Y (or to Z if Y is a bond or to Poly if Y and Z are bonds);

Y is a bond or a divalent aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group, wherein aliphatic, cycloaliphatic, aromatic, mixed The aliphatic, cycloaliphatic and/or aromatic moieties of the aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic bridging groups may be substituted by one or more halogen atoms;

wherein the aliphatic, cycloaliphatic or aromatic bridging group may have at least one of the following features (i) and/or (ii), mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic -aromatic bridging groups may have at least one of the following features (i), (ii) and/or (iii):

(i) at least one aliphatic, cycloaliphatic and/or aromatic moiety of an aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group; Non-adjacent groups -O-, -S-, -N(R ¹³ )-, -OC(=O)-, -C(=O)-O-, -N(R ¹³ )-C(=O) -, -C(=O)-N(R ¹³ )-, -OC(=O)-O-, -OC(=O)-N(R ¹³ )-, -N(R ¹³ )-C(= interrupted by O)-O- and/or -N(R ¹³ )-C(=O)-N(R ¹³ )-;

(ii) an aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group is —OH, —SH, —N(R ¹³ ) ₂ , -OC(=O)H, -C(=O)OH, -N(R ¹³ )-C(=O)H, -C(=O)-NHR ¹³ , -OC(=O)-OH, - having one or more substituents selected from the group consisting of OC(=O)-NHR ¹³ , -N(R ¹³ )-C(=O)-OH and -N(R ¹³ )-C(=O)-NHR ¹³ box;

(iii) the aliphatic, cycloaliphatic and/or aromatic moieties of the mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group are the groups -O-, -S-, - N(R ¹³ )-, -OC(=O)-, -C(=O)-O-, -N(R ¹³ )-C(=O)-, -C(=O)-N(R ¹³ ) )-, -OC(=O)-O-, -OC(=O)-N(R ¹³ )-, -N(R ¹³ )-C(=O)-O- or -N(R ¹³ )- bonded to each other via C(=O)-N(R ¹³ )-;

wherein each R ¹³ is independently hydrogen or C ₁ -C ₁₀ -alkyl;

Z is a bond or group -C(=O)-, ^# -C(=O)-O- ^* or ^# -C(=O)-N(R ¹³ )- ^* , when X and Y are bonds is; where ^# is the point of attachment to Y (or to X if Y is a bond or to O if X and Y are bonds), ^* is the point of attachment to Poly; or

Y is a bond and X is a group -C(=O)-, ^# -C(=O)-O- ^* or ^# -C(=O)-N(R ¹³ )- ^* where ^# is the point of attachment to O ), if it is a bond; or

When Y is a divalent aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group, a bond or group -O-, -S- , -N(R ¹³ )-, -C(=O)-, ^# -OC(=O)- ^* , ^# -C(=O)-O- ^* , ^# -N(R ¹³ )-C(= O)- ^* , ^# -C(=O)-N(R ¹³ )- ^* , ^# -OC(=O)-O- ^* , ^# -OC(=O)-N(R ¹³ )- ^* , ^# -N(R ¹³ )-C(=O)-O- ^* or ^# -N(R ¹³ )-C(=O)-N(R ¹³ )- ^* , where ^# is the point of attachment to Y;

n is 1 to 1000;

Poly is a residue derived from a polymer having a number average molecular weight of 200 to 10000;

Propargyl alcohol is a compound of formula II-poly:

wherein X, Y, Z, n and Poly are as defined above.

More preferably,

X is a bond or group -C(=O)- or ^# -C(=O)-N(R ¹³ )- ^* , where ^# is the point of attachment to O and ^* is to Y (or if Y is a bond) is the point of attachment to Z or to Poly when Y and Z are bonds;

Y is a bond or a divalent aliphatic or mixed aliphatic-cycloaliphatic bridging group having 1 to 10 carbon atoms, wherein the aliphatic or mixed aliphatic-cycloaliphatic bridging group may be substituted by one or more halogen atoms;

wherein the aliphatic bridging group may have at least one of the following features (i) and/or (ii), and the mixed aliphatic-cycloaliphatic bridging group may have at least one of the following features (i), (ii) and/or (iii) can be:

(i) the aliphatic and/or cycloaliphatic moiety of an aliphatic or mixed aliphatic-cycloaliphatic bridging group includes one or more non-adjacent groups -O-, -O-C(=O)-, -C(=O)-O-, and/or are interrupted by -O-C(=O)-O-;

(ii) the aliphatic or mixed aliphatic-cycloaliphatic bridging group bears one or more substituents selected from the group consisting of -OH, -O-C(=O)H and -C(=O)OH;

(iii) the aliphatic and/or cycloaliphatic moieties of the mixed aliphatic-cycloaliphatic bridging group are the groups -O-, -O-C(=O)-, -C(=O)-O- or -O-C(=O)-O bound to each other via ;

Z is a bond or a group -C(=O)-, when X and Y are bonds; or

when Y is a bond and X is a group -C(=O)-, it is a bond; or

when Y is a divalent aliphatic or mixed aliphatic-cycloaliphatic bridging group, a bond or group ^# -OC(=O)-;

Poly is a residue derived from poly-α-olefins or poly(meth)acrylates, in particular poly(meth)acrylates, specifically polymethacrylates.

In particular, -XYZ- taken together is -C(=O)-, ^# -CH ₂ -CH(OH)-CH ₂ -OC(=O)- ^* or ^# -C(=O)-NH-CH ₂ CH ₂ -OC(=O)- ^* , where ^# is the point of attachment to O and ^* is the point of attachment to Poly. If Poly is derived from poly(meth)acrylate in this case, then polymer I-poly is [-CH ₂ -CH-(ZYXO-CH ₂ -CH=(1,3-dioxolan-2-one-4-diyl) )] or [-CH ₂ -C(CH ₃ )-(ZYXO-CH ₂ -CH=(1,3-dioxolan-2-one-4-diyl)] repeating units.

among R ¹ derived from individual molecules and from polymers, from individual molecules; Particular preference is given to R ¹ derived from individual molecules as defined above.

catalyst

In one preferred embodiment, the bulky ligand of the silver catalyst is a ligand of formula III.

In another preferred embodiment, the bulky ligand of the silver catalyst is a ligand of formula IV.

Among these, ligand III is more preferable.

Preferably, in the bulky ligand of formula (III),

D is P or As,

R ² is monocyclic or polycyclic C ₃ -C ₄₀ -cycloalkyl, monocyclic or polycyclic C ₃ -C ₄₀ -cycloalkenyl, C ₆ -C ₄₀ -aryl and 3- to 40-membered saturated, a cyclic radical selected from the group consisting of partially unsaturated or maximally unsaturated mono- or polycyclic heterocyclic rings, wherein the cyclic radical may be bonded to D via an oxygen atom, wherein the cyclic radical is C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, phenyl optionally substituted by 1, 2, 3, 4 substituents R ²² , naphthyl optionally substituted by 1, 2, 3, 4 substituents R ²² , ring member as monocyclic 5- or 6-membered heteroaromatic containing 1, 2, 3 or 4 heteroatoms selected from the group consisting of N, O and S and optionally substituted by 1, 2 or 3 substituents R ²³ ; and fused bicyclic 8- to 10- containing 1, 2, 3 or 4 heteroatoms selected from the group consisting of N, O and S as ring members and optionally substituted by 1, 2 or 3 substituents R ²³ . may have one or more substituents selected from the group consisting of a membered heteroaromatic ring system,

here

each R ²² is independently C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, NR ²⁴ R ²⁵ wherein R ²⁴ and R ²⁵ are independently of each other hydrogen or C ₁ -C ₁₂ -alkyl; phenyl, naphthyl and monocyclic saturated, partially unsaturated or maximally unsaturated 5- or 6-membered heterocyclic containing 1, 2, 3 or 4 heteroatoms selected from the group consisting of N, O and S as ring members wherein the last three cyclic radicals are selected from the group consisting of 1, 2, 3, 4 or finally selected from the group consisting of halogen, C ₁ -C ₄ -alkyl and C ₁ -C ₄ -alkoxy may have 5 substituents;

each R ²³ independently has one of the meanings given for R ²² ;

R ³ and R ⁴ are independently of each other C ₁ -C ₆ -alkyl, monocyclic or polycyclic C ₃ -C ₄₀ -cycloalkyl, monocyclic or polycyclic C ₃ -C ₄₀ -cycloalkenyl and C ₆ -C ₁₀ -aryl is selected from the group consisting of.

More preferably,

D is P;

R ² is phenyl optionally substituted by 1, 2, 3, 4 substituents R ²² , ortho-biphenyl optionally substituted by 1, 2, 3, 4 substituents R ²² , 1, 2, 3, 4 naphthyl optionally substituted by substituent R ²² , ortho-binaphthyl optionally substituted by 1, 2, 3, 4 substituents R ²² , containing 1, 2 or 3 nitrogen atoms as ring member and containing 1, 2 or monocyclic 5- or 6-membered heteroaromatic optionally substituted by 3 substituents R ²³ , and containing 1, 2 or 3 or 4 nitrogen atoms as ring members, and 1, 2 or 3 substituents R ²³ is a fused bicyclic 8- to 10-membered heteroaromatic ring system optionally substituted by

here

each R ²² is independently C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, NR ²⁴ R ²⁵ , wherein R ²⁴ and R ²⁵ independently of each other are hydrogen or C ₁ -C ₁₀ -alkyl; phenyl optionally substituted by 1, 2, 3, 4 or 5 substituents selected from the group consisting of halogen, C ₁ -C ₄ -alkyl and C ₁ -C ₄ -alkoxy; and monocyclic saturated, partially unsaturated or maximally unsaturated 5- or 6-membered heterocyclic rings containing 1, 2 or 3 heteroatoms selected from the group consisting of N and O as ring members;

each R ²³ is independently phenyl optionally substituted by 1, 2, 3, 4 or 5 substituents selected from the group consisting of halogen, C ₁ -C ₄ -alkyl and C ₁ -C ₄ -alkoxy;

R ³ and R ⁴ are independently of each other selected from the group consisting of branched C ₃ -C ₆ -alkyl, monocyclic C ₃ -C ₆ -cycloalkyl, adamantyl, phenyl.

Specifically,

D is P;

R ² is phenyl substituted by NR ²⁴ R ²⁵ , wherein R ²⁴ and R ²⁵ independently of each other are hydrogen or C ₁ -C ₁₀ -alkyl, preferably C ₃ -C ₁₀ -alkyl; or ortho-biphenyl substituted by 1, 2, 3 or 4 substituents R ²² ,

here

each R ²² is independently C ₁ -C ₄ -alkyl and NR ²⁴ R ²⁵ (wherein R ²⁴ and R ²⁵ are independently of each other hydrogen or C ₁ -C ₁₀ -alkyl, preferably C ₃ -C ₁₀ -alkyl is selected from the group consisting of ).

In particular, the bulky ligand is selected from compounds of formulas A to W and mixtures thereof:

where Me is methyl, Cy is cyclohexyl, i-Pr is isopropyl, Ph is phenyl, and t-Bu is tert-butyl.

These ligands are known as Buchwald ligands. Many of these are, for example, DavePhos (A), MePhos (B), XPhos (D), tBuDavePhos (E), JohnPhos (G), PhDavePhos (J), CyJohnPhos (M), SPhos (O), RuPhos (Q) , CPhos (R), BrettPhos (S), AlPhos (T) and RockPhos (U) are commercially available.

In a specific embodiment, XPhos (a compound of formula D), a ligand of formula V, a ligand of formula W, or a mixture of V and W is used as ligand III. Very specifically, the compound of formula D (XPhos) is used.

In the ligand of formula IV, the double dot indicates that the ligand is a carbene. Therefore, Ligand IV is also called N-heterocyclic carbene ligand or NHC-ligand for short. A silver catalyst containing NHC ligand IV can be depicted as follows:

Preferably, in the ligand of formula IV, R ² and R ⁵ are independently of each other 1 selected from the group consisting of C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy and C ₃ -C ₆ -cycloalkyl; C ₆ -C ₁₀ -aryl optionally substituted by 2, 3, 4 or 5 substituents, Z is -CR ⁷ =CR ⁸ -, wherein R ⁷ and R ⁸ are independently of each other hydrogen or C ₁ -C ₆ -alkyl). In particular, R ² and R ⁵ are 2,6-diisopropylphenyl and Z is -CH=CH-.

R ⁶ is preferably C ₁ -C ₄₀ -alkyl, C ₂ -C ₄₀ -alkenyl, C ₃ -C ₁₀ -C ₁ -C ₆ -alkyl bearing a cycloalkyl ring, wherein C ₃ -C ₁₀ - the cycloalkyl ring may bear 1, 2, 3, 4 or 5 C ₁ -C ₆ -alkyl substituents; C ₁ -C ₄ -alkyl having a C ₆ -C ₁₀ -aryl ring, wherein the C ₆ -C ₁₀ -aryl ring is 1 selected from the group consisting of C ₁ -C ₆ -alkyl and C ₁ -C ₆ -alkoxy , which may have 2, 3, 4 or 5 substituents); and C ₆ -C ₁₀ -aryl which may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of C ₁ -C ₆ -alkyl and C ₁ -C ₆ -alkoxy . More preferably, R ⁶ is selected from the group consisting of C ₁ -C ₄₀ -alkyl, C ₂ -C ₄₀ -alkenyl and C ₁ -C ₄ -alkyl having a C ₃ -C ₆ -cycloalkyl ring. . Even more preferably, R ⁶ is from the group consisting of C ₁ -C ₃₀ -alkyl, C ₆ -C ₃₀ -alkenyl and C ₁ -C ₄ -alkyl bearing C ₃ -C ₆ -cycloalkyl rings, especially from C ₁ -C ₂₂ -alkyl and C ₁ -C ₄ -alkyl with C ₅ -C ₆ -cycloalkyl rings, specifically C ₁ -C ₂₀ -alkyl and C ₂ -C with cyclohexyl rings from ₄ -alkyl, very particularly from C ₈ -C ₁₈ -alkyl and C ₂ -C ₄ -alkyl having a cyclohexyl ring.

When R ⁶ is an alkyl group, the corresponding carboxylate R ⁶ -COO ^- is more preferably from 2 to 41 carbon atoms, even more preferably from 2 to 31 carbon atoms, in particular from 2 to 23 carbon atoms, specifically derived from natural or synthetic saturated fatty acids having from 2 to 21 carbon atoms, very specifically from 9 to 19 carbon atoms; When R ⁶ is an alkenyl group, the corresponding carboxylate R ⁶ -COO ^- is more preferably from a natural or synthetic unsaturated fatty acid having from 3 to 41 carbon atoms, even more preferably from 7 to 31 carbon atoms. is derived In the case where R ⁶ is an alkyl group, the carboxylate R ⁶ -COO ^- is especially from natural or synthetic saturated fatty acids having 2 to 23 carbon atoms, in particular from saturated fatty acids having 2 to 21 carbon atoms, very specifically It is derived from saturated fatty acids having 9 to 19 carbon atoms.

In a specific embodiment, R ⁶ is lipophilic and thus preferably has at least 2 carbon atoms. Thus, in this case, R ⁶ is preferably C ₂ -C ₄₀ -alkyl, C ₂ -C ₄₀ -alkenyl, C ₁ -C ₆ -alkyl bearing a C ₃ -C ₁₀ -cycloalkyl ring, wherein a C ₃ -C ₁₀ -cycloalkyl ring may bear 1, 2, 3, 4 or 5 C ₁ -C ₆ -alkyl substituents; C ₁ -C ₄ -alkyl having a C ₆ -C ₁₀ -aryl ring, wherein the C ₆ -C ₁₀ -aryl ring is 1 selected from the group consisting of C ₁ -C ₆ -alkyl and C ₁ -C ₆ -alkoxy , which may have 2, 3, 4 or 5 substituents); and C ₆ -C ₁₀ -aryl which may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of C ₁ -C ₆ -alkyl and C ₁ -C ₆ -alkoxy . More preferably, in this case, R ⁶ consists of C ₂ -C ₄₀ -alkyl, C ₂ -C ₄₀ -alkenyl and C ₁ -C ₄ -alkyl bearing C ₃ -C ₆ -cycloalkyl rings. selected from the group. Even more preferably, R ⁶ is from the group consisting of C ₆ -C ₃₀ -alkyl, C ₆ -C ₃₀ -alkenyl and C ₁ -C ₄ -alkyl bearing C ₃ -C ₆ -cycloalkyl rings, in particular from C ₆ -C ₂₂ -alkyl and C ₁ -C ₄ -alkyl with C ₅ -C ₆ -cycloalkyl rings, specifically C ₈ -C ₂₀ -alkyl and C ₂ -C with cyclohexyl rings from ₄ -alkyl, very particularly from C ₈ -C ₁₈ -alkyl and C ₂ -C ₄ -alkyl bearing a cyclohexyl ring.

The silver catalyst Ag1 of the process of the invention, as indicated above, comprises at least one bulky ligand selected from the group of ligands consisting of silver, a compound of formula III and a compound of formula IV, preferably a compound of formula III, and formula V It can be used in the form of a pre-formed metal complex comprising a lipophilic carboxylate ligand according to

Alternatively, the silver catalyst Ag1 is catalytically active by combining a silver pro-catalyst, which is a silver compound or silver salt containing no bulky ligand, with a compound of formula III, a carbene of formula IV, or a precursor of a carbene of formula IV in a reaction medium. Silver is formed in situ in the reaction medium by forming the complex Ag1. In case the silver pro-catalyst does not contain a lipophilic carboxylate ion V, the silver pro-catalyst can also be combined with the corresponding acid R ⁶ -C(=O)OH of the carboxylate V or with the formula R ⁶ -C ( =O)O ^- M ⁺ (where M ⁺ is the cation equivalent) with its salt.

A suitable precursor of the carbene of formula (IV) is its protonated form, represented by formula (VI), which is combined with a base:

wherein R ² , R ⁵ and Z are defined as described above and X ⁻ is an anionic equivalent.

Suitable bases for deprotonating the protonated forms of various NHC ligands according to formula VI are described in de Fremont et al., Coordination Chemistry Reviews 253 (2009) 876 to 881. Deprotonation of the protonated form of the NHC ligand can be carried out in ammonia or in a non-protic solvent such as THF or ether. Deprotonation requires anhydrous conditions and the use of strong bases with pK _a values greater than 14. Typically, potassium hydride or sodium hydride is used with a catalytic amount of tert-butoxide, but tert-butoxide itself, lithium aluminum hydride, n-butyllithium, methyllithium, tert-butyllithium, potassium hexamethyldisilazide (KHMDS) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) are also efficient alternatives.

Silver compounds useful as pro-catalysts include, for example, the formulas given as Ag(OAc) (OAc = acetate), AgF, AgNO ₃ , silver trifluoroacetate, Ag ₂ O, Ag ₂ CO ₃ and Ag(OOCR ⁶ ) Any silver salt with a lipophilic carboxylate ion according to V. When Ag(OAc), AgF, AgNO ₃ , silver trifluoroacetate, Ag ₂ O or Ag ₂ CO ₃ is used as pro-catalyst, the lipophilic carboxylate ligand can also be in the form of the free acid HOOCR ⁶ or The optional salt R ⁶ -C(=O)O ^- M ⁺ (where M ⁺ is the cation equivalent) must be added to the reaction medium. Suitable cation equivalents are metal cations such as alkali metal cations, for example Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ or Rb ⁺ , or alkaline earth metal cations such as Ca ²⁺ , Mg ²⁺ , Sr ²⁺ or Ba ² . ⁺ ; or an ammonium cation NR ₄ ⁺ , wherein each R is independently hydrogen, C ₁ -C ₁₀ -alkyl or C ₁ -C ₁₀ -alkoxy. Thus, a salt is, for example, M ₁ (OOCR ⁶ ), wherein M ₁ can be Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Rb ⁺ or NR ₄ ⁺ , or M ₂ is Ca ²⁺ , may be M ₂ (OOCR ⁶ ) ₂ , which may be Mg ²⁺ , Sr ²⁺ or Ba ²⁺ . Preferably, the pro-catalyst is Ag(OOCR ⁶ ).

In the case of in situ formation of the silver catalyst Ag1, the compound of formula III, carbene of formula IV or precursor of carbene of formula IV is suitably used in an amount of less than 2 mol per mol of silver present in the silver pro-catalyst . Preferably, the compound of formula III, carbene of formula IV or precursor of carbene of formula IV is from 0.2 to 1.8 mol, preferably from 0.3 to 1.5 mol, in particular from 0.4 to 1.2, per mol of silver present in the silver pro-catalyst mol, in particular 0.8 to 1.2 mol, very specifically used in approximately equimolar amounts with the silver present in the silver pro-catalyst.

Preferably, for practical and economic reasons, the catalyst is formed in situ in step a).

Based on the amount of propargyl alcohol of formula (II), the amount of silver catalyst Ag1 used in process step a) can vary within a wide range. Typically, the silver catalyst Ag1 is used in substoichiometric amounts relative to the propargyl alcohol of formula II. Typically, the amount of silver catalyst Ag1 is 50 mol % or less, frequently 20 mol % or less, in particular 10 mol % or less or 5 mol % or less or 3 mol %, based on the amount of propargyl alcohol of formula (II) is below. The silver catalyst Ag1 in step a), based on the amount of propargyl alcohol of formula II, is preferably from 0.001 to 50 mol%, more preferably from 0.001 to 20 mol%, in particular from 0.005 to 10 mol%, specifically as 0.01 to 5 mol %, very specifically 0.05 to 3 mol %. The above given amounts of catalyst represent the amount of silver contained therein.

menstruum

In the process of the invention, solvents L1 and L2 are used. A “solvent” is a substance that dissolves a solute (a chemically different liquid, solid, or gas) to form a solution. A solution is a homogeneous mixture in which a gaseous, liquid or solid solute is dissolved in a solvent. A homogeneous mixture, finally, consists of two or more substances, wherein the solute particles are invisible to the naked eye and do not scatter light. In the text, solvents L1 and L2 are liquids at 20°C. Solvents L1 and L2 have different polarities and therefore have different solvating capacities for different solutes. Solvent L1 has weak solvating ability to non-polar starting materials or products, and solvent L2 has weak solvating ability to polar starting materials or products. Thus, in the present context, the term “solvent” is not limited in its true sense to a compound or medium in which all starting materials, catalyst components and products are dissolved. A solvent is more generally understood as a dispersion medium which dissolves (in the true sense) only a portion of the starting material, catalyst component or product.

Solvents L1 and L2 used in the process of the present invention have a miscibility gap at 1013 mbar, at least 20 to 30°C. By "miscibility gap" it is meant that the mixture of solvents L1 and L2 is not stable and demixes to form two separate phases. One of the two phases consists essentially of solvent L1 and the other consists essentially of solvent L2. "Essentially" means that the phase contains less than 10% by weight, preferably less than 5% by weight, of other solvents, ie solvents that are not major components, relative to the total weight of solvents L1 and L2. At 20° C., solvent L1 has a miscibility of less than 5 g per liter of L2 in solvent L2, preferably less than 2 g per liter of L2, in particular less than 1 g per liter of L2, and solvent L2 has a miscibility of less than 5 g per liter of L1 in solvent L1. It has a miscibility of less than g, preferably less than 2 g per liter of L1, in particular less than 1 g per liter of L1. Miscibility refers to the formation of a homogeneous mixture in which no phase separation occurs.

Preferably, the solvents L1 and L2 used in the process of the invention are at 1013 mbar, at least 20 to 80°C, more preferably at 1013 mbar, at least 15 to 100°C, in particular at 1013 mbar, wherein the solvent is a liquid There is a miscibility gap over the entire temperature range.

Preferably, the solvent L1 is a polar aprotic solvent having a dipole moment of at least 10·10 ^-30 C·m, in particular at least 11·10 ⁻³⁰ C·m.

Preferably, solvent L2 is a non-polar solvent having a dipole moment of at most 2·10 ^-30 C·m, preferably at most 1·10 ⁻³⁰ C·m, in particular 0 C·m.

Preferably, solvent L1 is a polar aprotic solvent having a dipole moment of at least 10·10 ^-30 C·m and solvent L2 is a non-polar solvent having a dipole moment of at most 2·10 ^-30 C·m .

More preferably, solvent L1 is a polar aprotic solvent having a dipole moment of at least 11·10 ^-30 C·m, and solvent L2 is a non-polar solvent having a dipole moment of at most 1·10 ^-30 C·m. to be.

In particular, solvent L1 is a polar aprotic solvent having a dipole moment of at least 11·10 ^-30 C·m, and solvent L2 is a non-polar solvent having a dipole moment of 0 C·m.

The solvent L1 is preferably selected from the group consisting of amides, ureas, nitriles, sulfoxides, sulfones, carbonates, nitro compounds and mixtures thereof.

Examples of suitable amides are formamide, N-methylformamide, N,N-dimethylformamide and N,N-dimethylacetamide.

Examples of suitable ureas are tetramethylurea, N,N-dimethylimidazolinone and N,N-dimethylpropyleneurea.

Examples of suitable nitriles are acetonitrile, propionitrile and benzonitrile.

An example of a suitable sulfoxide is dimethylsulfoxide.

An example of a suitable sulfene is sulfolane.

Examples of suitable carbonates are dimethyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate.

Examples of suitable nitro compounds are nitromethane and nitrobenzene.

L1 is more preferably formamide, N-methylformamide, N,N-dimethylformamide (DMF), N,N-dimethylacetamide, tetramethylurea, N,N-dimethylimidazolinone, N, N-dimethylpropyleneurea, acetonitrile, propionitrile, benzonitrile, dimethylsulfoxide, sulfolane, dimethylcarbonate, diethylcarbonate, ethylene carbonate, propylene carbonate, nitromethane, nitrobenzene and is selected from the group consisting of mixtures thereof.

In a specific embodiment, L1 is acetonitrile or DMF, and more particularly acetonitrile.

The solvent L2 is preferably selected from the group consisting of alkanes, cycloalkanes, C ₁ -C ₂ -alkyl esters of C ₁₂ -C ₂₀ -fatty acids and mixtures thereof.

Examples of suitable alkanes are C ₅ -C ₁₅ -alkanes such as pentane, hexane, heptane, octane, nonane, decane, dodecane, tetradecane, pentadecane, structural isomers thereof and mixtures thereof.

Examples of suitable cycloalkanes are C ₅ -C ₈ -cycloalkanes which may bear C ₁ -C ₂ -alkyl substituents, such as cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, cyclooctane and the like.

Examples of suitable C ₁ -C ₂ -alkyl esters of C ₁₂ -C ₂₀ -fatty acids are methyllaurate, ethyllaurate, methylmyristate, ethylmyristate, methylpalmitate, ethylpalmitate, methylstearate, ethylstearate rate, methyl arachidate and ethyl arachidate.

More preferably, the solvent L2 is a C ₅ -C ₁₄ -alkane, C ₁ -C 2 -C ₅ -C ₈ -cycloalkane, which may bear C 1 -C ₂ -alkyl substituents, C ₁₂ -C ₂₀ -C ₁ -C of fatty acids ₂ -alkyl esters and mixtures thereof. Even more preferably, the solvent L2 is selected from the group consisting of C ₆ -C ₁₂ -alkanes, C ₅ -C ₆ -cycloalkanes which may bear a methyl substituent, methyl esters of C ₁₆ -C ₂₀ -fatty acids and mixtures thereof. is chosen In particular, the solvent L2 is selected from the group consisting of pentane, hexane, heptane, octane, nonane, decane, dodecane, cyclopentane, cyclohexane, and mixtures thereof.

In a specific embodiment, L2 is cyclohexane, hexane or decane, more specifically cyclohexane or decane, and very specifically cyclohexane.

In certain embodiments,

- solvent L1 is acetonitrile, solvent L2 is C ₅ -C ₁₄ -alkanes, C ₅ -C ₈ -cycloalkanes which may carry C ₁ -C ₂ -alkyl substituents, and saturated C ₁₂ -C ₂₀ fatty acids selected from the group consisting of C ₁ -C ₂ -alkyl esters; or

- solvent L1 is dimethylformamide, solvent L2 is C ₅ -C ₁₄ -alkanes, C ₅ -C ₈ -cycloalkanes which may carry C ₁ -C ₂ -alkyl substituents, and saturated C ₁₂ -C ₂₀ fatty acids C ₁ -C ₂ -alkyl esters of

more particularly,

- solvent L1 is acetonitrile and solvent L2 is from the group consisting of C ₅ -C ₁₂ -alkanes, C ₅ -C ₈ -cycloalkanes which may bear a methyl substituent, and methyl esters of saturated C ₁₆ -C ₂₀ fatty acids. selected; or

- solvent L1 is dimethylformamide, solvent L2 is the group consisting of C ₅ -C ₁₂ -alkanes, C ₅ -C ₈ -cycloalkanes which may have methyl substituents, and methyl esters of saturated C ₁₆ -C ₂₀ fatty acids is selected from

more particularly,

- solvent L1 is acetonitrile and solvent L2 is selected from the group consisting of C ₅ -C ₁₂ -alkanes and C ₆ -C ₈ -cycloalkanes; or

- solvent L1 is dimethylformamide and solvent L2 is selected from the group consisting of C ₅ -C ₁₂ -alkanes and C ₅ -C ₈ -cycloalkanes.

Specifically,

- solvent L1 is acetonitrile and solvent L2 is cyclohexane; or

- solvent L1 is acetonitrile and solvent L2 is hexane; or

- solvent L1 is acetonitrile and solvent L2 is octane; or

- solvent L1 is acetonitrile and solvent L2 is decane; or

- solvent L1 is acetonitrile and solvent L2 is dodecane; or

- solvent L1 is dimethylformamide and solvent L2 is cyclohexane; or

- solvent L1 is dimethylformamide and solvent L2 is hexane; or

- solvent L1 is dimethylformamide and solvent L2 is octane; or

- solvent L1 is dimethylformamide and solvent L2 is decane; or

- Solvent L1 is dimethylformamide and solvent L2 is dodecane.

very specifically,

- solvent L1 is acetonitrile and solvent L2 is cyclohexane; or

- solvent L1 is acetonitrile and solvent L2 is decane; or

- Solvent L1 is dimethylformamide and solvent L2 is hexane.

Among these, it is preferable that the solvent L1 is acetonitrile and the solvent L2 is cyclohexane or decane.

Propargyl alcohol in step a) is preferably 0.1 to 25% by weight, more preferably 0.5 to 20% by weight, in particular 1 to 20% by weight, relative to the total weight of all solvents used in step a), For example, it is present in an amount of 1 to 15% by weight.

The CO ₂ used for the carboxylation-cyclization reaction can be used in pure form or, if desired, also in the form of a mixture with other, preferably inert gases, such as nitrogen or argon. It is preferred to use CO ₂ in undiluted form.

The reaction is typically carried out at a CO ₂ pressure in the range from 0.1 to 200 bar, preferably in the range from 1 to 100 bar, more preferably in the range from 5 to 80 bar, in particular from 10 to 70 bar. When CO ₂ is in undiluted form, the pressure is applied by CO ₂ . In this case, the reaction is typically carried out at a CO ₂ pressure in the range of 0.1 to 200 bar, preferably in the range of 1 to 100 bar, more preferably in the range of 5 to 80 bar, in particular 10 to 70 bar. do.

Under certain conditions, if the reaction conditions are such that CO ₂ is a liquid (eg pressure greater than 57.3 bar at 20°C) or exists in its supercritical phase (pressure greater than 73.8 bar at temperature greater than 31°C) , CO ₂ can also act as an additional solvent for the two liquid phases formed by solvents L1 and L2 (if step a) is carried out in the presence of solvent L2 or act as a solubilizer.

Method step a) can be carried out over a wide temperature range. The reaction can be carried out at a temperature in the range of 0 to 150 °C, but considering that high temperature is not essential, the reaction is preferably 0 to 100 °C, more preferably 10 to 80 °C, especially 10 to 40 °C It is carried out at a temperature in the range of °C.

The reaction can in principle be carried out continuously, semi-continuously or discontinuously. A continuous process is preferred.

The reaction can in principle be carried out in all reactors known by the person skilled in the art for reactions of this type, and the reactors will be selected accordingly. Suitable reactors are described and discussed in the relevant prior art, for example in the appropriate research papers and references, such as are mentioned in US 6,639,114 at column 16, lines 45-49. Preferably, an autoclave, which may have an internal stirrer and an internal lining, is used for the reaction.

The composition obtained in the carboxylation-cyclization reaction of the present invention comprises an unsubstituted exo-vinylidene carbonate, ie a cyclic carbonate of the formula Ia or Ib.

After completion of step a), the pressure is released before steps b1) (if performed), b2) (if performed) and c) follow.

Step b1) should be carried out if solvent L2 was not used in step a).

If in step a) a solvent mixture containing L1 and L2 is used, it is nevertheless possible to carry out step b2) under certain circumstances; That is, it may be advantageous to add additional solvent L2, for example if the mixture contains too little L2 to allow efficient phase separation. The ideal mixing ratio of the solvents L1 and L2 depends on the specific solvents L1 and L2, the specific starting materials, the catalyst, their respective concentrations and the phase separation method, and can be determined by one of ordinary skill in the art.

A suitable amount of solvent L2 added in step b1) or b2) is that in step c) solvent L1 and solvent L2 are preferably 80:20 to 20:80, more preferably 70:30 to 30:70, in particular 60 It is an amount such that it is present in a total weight ratio of :40 to 40:60.

In one embodiment of the invention, no solvent L2 is used in step a) and step b1) is performed (in this case step b2) is naturally omitted).

In another embodiment of the invention, in step a) a solvent mixture containing L1 and L2 is used; If the amount of L2 is not too small to enable efficient phase separation, step b2) can be omitted; If so, step b2) is performed.

In step c), the two organic liquid phases can be separated from each other and the non-polar organic phase enriched in silver catalyst can be recycled as catalyst to the carboxylation reaction of step a).

The two liquid phases are separated by phase separation, usually by weight. For example, it is described, for example, in E. Mueller et al., "Liquid-Liquid Extraction" in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH&Co KGaA, DOI: 10.1002/14356007.b03_06, chapter 3 "Apparatus"]. can be performed.

Phase separation can be carried out on a laboratory scale, for example with a separatory funnel; On an industrial scale, countercurrent extraction devices such as mixed-settler devices, extraction columns, stirred extraction columns, continuous packed bed liquid liquid extraction devices and the like are suitable.

Steps b1)/b2) and c) may be repeated once or several times. For example, after phase separation in step c), L2 can be added to the separated phase containing L1 to obtain a more complete extraction of catalyst Ag1. However, in general, the separation is sufficiently smooth that it is not necessary to repeat steps b1)/b2) and c).

According to the invention, step c) results in the separation of the catalyst from the cyclic carbonate by the use of two organic solvents with miscibility differences. The silver catalyst Ag1 is enriched in the less polar solvent and the cyclic carbonate is enriched in the more polar solvent.

The enrichment of silver catalyst Ag1 in a less polar solvent means a partition coefficient of silver catalyst Ag1 of >1:

P = [concentration of silver catalyst Ag1 in non-polar organic phase]/[concentration of silver catalyst Ag1 in polar organic phase]

The partition coefficient is preferably >2, particularly preferably >5.

Enrichment of product Ia or Ib or mixture thereof in a polar solvent means a partition coefficient of product Ia or Ib or mixture thereof >1:

P = [concentration of product la or lb in polar organic phase]/[concentration of product la or lb in non-polar organic phase]

The partition coefficient is preferably >2, particularly preferably >5.

Thus, the product phase obtained in step c) contains more than 50% by weight, preferably more than 66.7% by weight, in particular more than 83.3% by weight of the cyclic carbonate I formed in step a), and the catalyst phase contains more than 50% by weight , preferably more than 66.7% by weight, in particular more than 83.3% by weight of silver catalyst.

If desired, the cyclic carbonate I can be isolated from the product phase [step d)]. For example, the product can be obtained by evaporating the solvent from the polar organic phase and, if desired, the solvent can be recycled to the carboxylation reaction. This method of isolation is particularly advantageous for syntheses carried out on an industrial scale. Polar organic solvents can also be used to further reduce the amount of product in the non-polar phase by countercurrent extraction. Conversely, a certain amount of non-polar solvent from the non-polar organic solvent phase is removed by evaporation and likewise used to reduce the silver content in the polar organic phase by counter-current-extraction, allowing greater recycling of the silver catalyst. .

The recycled silver catalyst can be reused in step a) with a satisfactory conversion after the first turnover. Even after several turnovers, the catalytic activity is still satisfactory.

Naturally, the work-up of the polar organic phase of the process of the invention and the isolation of the cyclic carbonates of formula Ia or Ib can also be carried out in another customary manner, for example by filtration or aqueous extraction work-up, Isolation via evaporation of a polar solvent is the most economical and simplest route, at least on an industrial scale. The cyclic carbonates of formula Ia or Ib or mixtures thereof are generally obtained in sufficient purity with the exclusion of further purification steps by applying such measures or combinations thereof. Alternatively, further purification may be accomplished by methods commonly used in the art, such as recrystallization.

The invention is illustrated by the following examples.

Example

Numerical values in percent are based on percent by weight, respectively, unless expressly stated otherwise.

General Information

All chemicals and solvents were purchased from Sigma-Aldrich or ABCR and used without further purification.

¹ H and ¹³ C NMR spectra were recorded with a Bruker Avance 200 MHz and 400 MHZ spectrometer, and the residual proton ( ¹ H) or carbon ( ¹³ C) resonance peaks of the solvent were referenced. Chemical shifts (δ) are reported in ppm.

Abbreviations used:

XPhos = 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl

THF = tetrahydrofuran

DMF = N,N-dimethylformamide

Et ₂ O = diethyl ether

I. Synthesis of Ligands V and W

The title compound was obtained via a synthesis modified from that described in Synlett, 2017, 28, 2891-2895 (SI). 2-Bromoaniline (1.17 mL; 10.35 mmol), N,N-diisopropylethylamine (5.41 mL; 31.04 mmol) and 1-bromooctane (5.36 mL; 31.05 mmol) were mixed in a pressure tube with anhydrous DMF (10 mL) was added. The tube was hermetically sealed and heated at 120° C. for 48 h. The reaction was cooled to room temperature and diluted with petroleum ether/ethyl acetate (1:1 v/v; 100 mL). The organic phase was mixed with water (3 x 100 mL), 10% aq. Na ₂ CO ₃ (100 mL) and brine (100 mL) and dried over Na ₂ SO ₄ . The solution was evaporated to dryness and purified by silica column chromatography using petroleum ether as eluent. The product was obtained as a colorless oil (2.63 g; 64%).

¹ H NMR (300 MHz, CDCl ₃ ): δ = 7.55 (dd, J = 7.9, 1.5 Hz, 1H, H _Ar ), 7.22 (ddd, J = 8.1, 7.6, 1.9, 1H, H _Ar ), 7.09 ( dd, J = 8.0, 1.6 Hz, 1H, H _Ar ), 6.92-6.83 (m, 1H, H _Ar ), 3.06-2.95 (m, 4H, CH ₂ N), 1.50-1.35 (m, 4H, CH ₂ ) ), 1.35-1.16 (m, 20H, CH ₂ ), 0.91-0.79 (m, 6H, CH ₃ ).

¹³ C NMR (75 MHz, CDCl ₃ ): δ 149.8, 133.7, 127.5, 124.2, 124.2, 122.3, 53.5, 31.9, 29.5, 29.3, 27.2, 27.0, 22.7, 14.1.

HRMS (ESI): calculated m/z for C ₂₂ H ₃₈ BrN: 396.2260 [M+H] ⁺ ; Actual value 396.2261.

2. Synthesis of Ligand V

The title compound was prepared according to J. Org. Chem., 2000, 65, 5334-5341]. Mg turning (126 mg; 5.17 mmol), 2-bromo-N,N-dioctylaniline obtained from Example 1 (991 mg, 2.50 mmol) and THF (5 mL) were combined with a stirrer bar and a reflux condenser To an oven-dried 25 mL three neck flask was added under argon. 1,2-dibromoethane (38 μL; 0.44 mmol) in THF (1 mL) was added dropwise via cannula over 5 min, and the mixture was brought to 50° C. for 5 min and then brought to reflux for an additional 16 h. heated. The mixture was cooled to 60 °C. 1-Bromo-2-chlorobenzene (252 μL; 2.85 mmol) was added dropwise over 10 min and the mixture was heated at 60° C. for 2 h. After cooling to room temperature, CuCl (282 mg; 2.59 mmol) was added followed by dropwise addition of a solution of chlorodicyclohexylphosphine (0.57 mL; 2.59 mmol) in THF (1 mL). After the mixture was stirred for an additional 16 h, the suspension was diluted with petroleum ether/ethyl acetate (1:1; 70 mL), 30% NH ₄ OH (25 mL) and brine (25 mL) and the mixture was stirred for 10 min stirred for a while. The organic phase was collected and washed repeatedly with 5 mL portions of 30% NH ₄ OH until the aqueous phase became colorless. The organic phase was further washed with water (10 mL) and brine (5 mL) and dried over Na ₂ SO ₄ . The solvent was removed in vacuo and the residue was columned on silica using a hexanes/diethyl ether solvent gradient (1:0 hexanes/Et ₂ O to 19:1). The obtained pale yellow viscous oil (553 mg; 43% crude yield) contained the desired Ligand V, Ligand W and unidentified phosphine complex as main products in a ratio of approximately 1:0.24:0.12. The pure product was obtained after further purification by gradient silica column chromatography using dichloromethane/acetone as eluent (94 mg; 7%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.60-7.47 (m, 1H), 7.34-7.17 (m, 4H), 7.05-6.96 (m, 2H), 6.95-6.87 (m, 1H), 2.82 2.67 (m, 4H), 2.09-0.94 (m, 46H), 0.87 (m, 6H).

¹³ C NMR (75 MHz, CDCl ₃ ): δ 149.6 (d, J _CP = 30.7 Hz), 149.6, 136.2 (d, J _CP = 5.8 Hz), 135.1 (d, J _CP = 20.2 Hz), 133.4 (d , J _CP = 3.8 Hz), 132.7 (d, J _CP = 3.2 Hz), 131.3 (d, J _CP = 5.9 Hz), 127.9, 127.6, 125.9, 120.0, 120.0, 52.6, 37.1 (d, J _CP = 16.3) Hz), 33.9 (d, J _CP = 14.1 Hz), 31.9, 30.7 (d, J _CP = 11.3 Hz), 30.6 (d, J _CP = 17.5 Hz), 30.2 (d, J _CP = 12.7 Hz), 30.0 (d, J _CP = 8.5 Hz), 29.6, 29.4, 28.0 (d, J _CP = 7.5 Hz), 27.8 (d, J _CP = 10.5 Hz), 27.5, 27.4 (d, J _CP = 9.3 Hz), 27.3 (d, J _CP = 11.7 Hz), 27.2, 26.7, 26.6, 22.8, 14.2.

³¹ P NMR (122 MHz, CDCl ₃ ): δ -11.3.

HRMS (ESI): calculated m/z for C ₄₀ H ₆₄ NPs: 590.4849 [M+H] ⁺ ; Found 590.4850.

3. Synthesis of Ligand W

Mg turning (39 mg; 1.60 mmol), 2-bromo-N,N-dioctylaniline (496 mg, 1.25 mmol) and THF (8 mL) were mixed with an oven-dried 25 mL equipped with a stirrer bar and a reflux condenser. It was added under argon to a three-necked flask. 1,2-dibromoethane (19 μL; 0.22 mmol) in THF (1 mL) was added dropwise via cannula over 5 min and the mixture was brought to 50° C. for 5 min and then to reflux for an additional 3 h. heated. The mixture was cooled to room temperature and CuCl (141 mg; 1.43 mmol) was added followed by dropwise addition of a solution of chlorodicyclohexylphosphine (0.29 mL; 1.30 mmol) in THF (1 mL). After the mixture was stirred for an additional 16 h, the suspension was diluted with petroleum ether/ethyl acetate (1:1; 40 mL), 30% NH ₄ OH (10 mL) and brine (10 mL) and the mixture was stirred for 10 min stirred for a while. The organic phase was collected and washed repeatedly with 5 mL portions of 30% NH ₄ OH until the aqueous phase became colorless. The organic phase was further washed with water (10 mL) and brine (5 mL) and dried over Na ₂ SO ₄ . The solvent was removed in vacuo and the residue was columned on silica using a dichloromethane/acetone solvent gradient (1:0 CH ₂ Cl ₂ /acetone → 19:1). The product was isolated as a colorless, viscous oil (221 mg; 34%). Oxidized phosphine was also detected by ³¹ P NMR and HRMS (<4% of samples).

¹ H NMR (500 MHz, CDCl ₃ ): δ 7.38 (d, J = 7.3 Hz, 1H), 7.24 (t, J = 7.5 Hz, 1H), 7.11-7.04 (m, 1H), 7.01 (t, J ) = 7.2 Hz, 1H), 3.10-3.02 (m, 4H), 1.94-1.85 (m, 2H), 1.84-1.71 (m, 4H), 1.65 (br s, 4H), 1.58-1.52 (m, 2H) , 1.40 (br s, 2H), 1.33-1.00 (m, 30H), 0.86 (t, J = 6.7 Hz, 6H).

¹³ C NMR (75 MHz, CDCl ₃ ): δ 157.8 (d, J _CP = 19.4 Hz), 133.4 (d, J _CP = 3.5 Hz), 133.2 (d, J _CP = 16.9 Hz), 128.6, 122.7 (d) , J _CP = 3.6 Hz), 122.6, 54.7 (d, J _CP = 5.8 Hz), 34.9 (d, J _CP = 15.1 Hz), 31.9, 30.5 (d, J _CP = 16.5 Hz), 29.8 (d, J _CP = 11.0 Hz), 29.6, 29.3, 27.5, 27.5-27.3 (m), 26.6, 26.4, 22.7, 14.1.

³¹ P NMR (122 MHz, CDCl ₃ ): δ -13.2.

II. Synthesis of cyclic carbonates

General reaction procedure

A. Addition of solvent L2 after carboxylation reaction:

An 80 mL steel autoclave was charged with propargyl alcohol (II) (5.0 mmol), silver salt, bulky donor ligand and polar organic solvent L1.

The reaction mixture was pressurized with CO ₂ and stirred at room temperature for 18 h. The CO ₂ overpressure was then carefully released and the catalyst was extracted with a non-polar organic solvent L2. After phase separation, the conversion of propargyl alcohol in both phases and the formation of the product was determined by ¹ H-NMR spectroscopy. The silver content in both phases was determined by ICP-MS.

Example 1:

alkynol: propargyl alcohol (R ¹ =H); 280 mg (5 mmol)

Silver salt: silver neodecanoate [Ag(C ₉ H ₁₉ C(O)O)]; 14 mg (0.05 mmol)

Bulk donor ligands: XPhos; 23.8 mg (0.05 mmol)

Polar organic solvent L1: acetonitrile; 10 mL

Non-polar organic solvent: cyclohexane

CO ₂ pressure: 20 bar

After the reaction, the conversion of propargyl alcohol to the corresponding exo-vinylidenecarbonate was determined to be 99% by NMR. The reaction mixture was extracted with cyclohexane (10 mL) as a non-polar organic solvent L2. According to ¹ H-NMR of the solvent fraction, exo-vinylidenecarbonate remained in the acetonitrile phase. The silver content was 370 mg/kg in the non-polar organic phase and 55 mg/kg in the polar organic phase (P=6.7).

Example 2:

alkynol: propargyl alcohol (R ¹ =H); 280 mg (5 mmol)

Silver salt: silver neodecanoate [Ag(C ₉ H ₁₉ C(O)O)]; 14 mg (0.05 mmol)

Bulk donor ligands: XPhos; 23.8 mg (0.05 mmol)

Polar organic solvent L1: acetonitrile; 10 mL

Non-polar organic solvent: cyclohexane

CO ₂ pressure: 20 bar

After the reaction, the conversion of propargyl alcohol to the corresponding exo-vinylidenecarbonate was determined to be 99% by NMR. The reaction mixture was extracted with cyclohexane (2*5 mL) as a non-polar organic solvent L2. According to ¹ H-NMR of the solvent fraction, exo-vinylidenecarbonate remained in the acetonitrile phase. After removal of all volatiles from the combined cyclohexane fractions and redissolving the remaining catalyst residue in acetonitrile (10 ml) and addition of fresh propargyl alcohol (but no additional silver or bulky ligands) It was reused for carboxylation under the same conditions as described above. The conversion to exo-vinylidene carbonate according to ¹ H-NMR spectroscopy was again 99%.

Example 3:

alkynol: propargyl alcohol (R ¹ =H); 280 mg (5 mmol)

Silver salts: silver stearate [Ag(C ₁₇ H ₃₅ C(O)O)]; 19.6 mg (0.05 mmol)

Bulk donor ligands: XPhos; 23.8 mg (0.05 mmol)

Polar organic solvent L1: acetonitrile; 10 mL

Non-polar organic solvent: Decane

CO ₂ pressure: 20 bar

After the reaction, the conversion of propargyl alcohol to the corresponding exo-vinylidenecarbonate was determined to be 99% by NMR. A 2 mL aliquot of the reaction solution was taken and extraction was performed with decane (2 mL) as a non-polar solvent L2. The silver content was 390 mg/kg in the non-polar organic phase and 50 mg/kg in the polar organic phase (Ρ = 7.8).

Example 4:

alkynol: propargyl alcohol (R ¹ =H); 280 mg (5 mmol)

Silver salt: silver cyclohexanebutyrate [Ag(cyclohexyl-(CH ₂ ) ₃ -C(O)O)]; 13.9 mg (0.05 mmol)

Bulk donor ligands: XPhos; 23.8 mg (0.05 mmol)

Polar organic solvent L1: acetonitrile; 10 mL

Non-polar organic solvent: cyclohexane

CO ₂ pressure: 20 bar

After the reaction, the conversion of propargyl alcohol to the corresponding exo-vinylidenecarbonate was determined to be 99% by NMR. A 2 mL aliquot of the reaction solution was taken and extraction was performed with cyclohexane (2 mL) as a non-polar solvent L2. The silver content was 390 mg/kg in the non-polar organic phase and 65 mg/kg in the polar organic phase (Ρ = 6.0).

Example 5:

alkynol: compound II wherein R ¹ = —CH ₂ —O—CH ₂ —CH(OH)—CH ₂ —OC(CH ₃ ) ₃ ; 1.08 g (5 mmol)

Silver salt: silver neodecanoate [Ag(C ₉ H ₁₉ C(O)O)]; 27.9 mg (0.10 mmol)

Bulk donor ligands: XPhos; 47.7 mg (0.10 mmol)

Internal standard: mesitylene 232 μL (1.67 mmol)

Polar organic solvent L1: acetonitrile; 10 mL

Non-polar organic solvent: cyclohexane

CO ₂ pressure: 20 bar

After all reagents and L1 were added, an aliquot of the mixture was diluted with CDCl ₃ to determine t0 by ¹ H NMR. The procedure described for Example 2 was followed, using cyclohexane as the non-polar solvent L2. After the reaction, the conversion of propargyl alcohol to the corresponding exo-vinylidenecarbonate was determined to be 76% by NMR. Upon recycle, the conversion to exo-vinylidenecarbonate was determined to be 67% by ¹ H NMR. The silver content was 1200 mg/kg in the non-polar organic phase and 310 mg/kg in the polar organic phase (Ρ = 43.9).

Example 6:

Alkynol: R ¹ =4,4'-((((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(2-hydroxypropane-3,1-diyl )) bis(oxy))bis(but-2-yn-1-ol), compound II (= a compound of formula II-bis, wherein A has the formula:

500 mg (0.97 mmol)

Silver salt: silver neodecanoate [Ag(C ₉ H ₁₉ C(O)O)]; 14 mg (0.05 mmol)

Bulk donor ligands: XPhos; 23.8 mg (0.05 mmol)

Polar organic solvent L1: acetonitrile; 10 mL

Non-polar organic solvent: cyclohexane

CO ₂ -Pressure: 20 bar

After the reaction, the conversion of propargyl alcohol to the corresponding bis exo-vinylidenecarbonate was determined to be 99% by NMR. The reaction mixture was extracted with cyclohexane (2*5 mL) as a non-polar organic solvent L2. According to ¹ H-NMR of the solvent fraction, exo-vinylidenecarbonate remained in the acetonitrile phase. The silver content was 100 mg/kg in the non-polar organic phase and 35 mg/kg in the polar organic phase (Ρ = 2.9).

Example 7:

Alkynol: R ¹ =4,4'-((((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(2-hydroxypropane-3,1-diyl )) compound II, which is bis(oxy))bis(but-2-yn-1-ol); 500 mg (0.97 mmol)

Silver salt: silver neodecanoate [Ag(C ₉ H ₁₉ C(O)O)]; 14 mg (0.05 mmol)

Bulk donor ligands: XPhos; 23.8 mg (0.05 mmol)

Polar organic solvent L1: dimethylformamide; 10 mL

Non-polar organic solvent: Hexane

CO ₂ -Pressure: 20 bar

After the reaction, the conversion of propargyl alcohol to the corresponding bis exo-vinylidenecarbonate was determined to be 56% by NMR. The reaction mixture was extracted with hexanes (2*5 mL) as a non-polar organic solvent L2. According to ¹ H-NMR of the solvent fraction, exo-vinylidenecarbonate remained in the acetonitrile phase.

B. Addition of solvent L2 in the carboxylation reaction:

An 80 mL steel autoclave was charged with propargyl alcohol (II) (5.0 mmol), silver salt, bulky donor ligand, polar organic solvent L1 and non-polar organic solvent L2. For the recycle experiment, the non-polar organic solvent L2 phase from the previous reaction, containing the silver catalyst, was charged to the autoclave and fresh polar organic solvent as well as propargyl alcohol were added. The reaction mixture was pressurized with CO ₂ and stirred at room temperature for 18 h. The CO ₂ overpressure was then carefully released. After phase separation, the conversion of propargyl alcohol in both phases and the formation of the product was determined by ¹ H-NMR spectroscopy. The silver content in both phases was determined by ICP-MS.

Example 8:

alkynol: propargyl alcohol (R ¹ =H); 280 mg (5 mmol)

Silver salt: silver neodecanoate [Ag(C ₁₀ H ₁₉ O ₂ ]; 14 mg (0.05 mmol)

Bulk donor ligands: XPhos; 23.8 mg (0.05 mmol)

Polar organic solvents: acetonitrile; 5 mL

Non-polar organic solvents: cyclohexane; 5 mL

CO ₂ -Pressure: 20 bar

After the reaction, the conversion of propargyl alcohol to the corresponding exo-vinylidenecarbonate was determined to be 91% by NMR. According to ¹ H-NMR of the solvent fraction, exo-vinylidenecarbonate could only be detected on acetonitrile. After phase separation, the cyclohexane phase containing the silver catalyst was reused for carboxylation under the same conditions as described above, after addition of 280 mg of propargyl alcohol and 5 mL of acetonitrile. The conversion to exo-vinylidenecarbonate according to ¹ H-NMR spectroscopy in the second run with recycled catalyst was 96%.

Example 9:

alkynol: propargyl alcohol (R ¹ =H); 280 mg (5 mmol)

Silver salt: silver neodecanoate [Ag(C ₉ H ₁₉ C(O)O)]; 14.0 mg (0.05 mmol)

Bulk donor ligands: compounds of formula V (actually obtained in 1.2, a mixture of V and W and unknown phosphine ligand in a ratio of approximately 1.0:0.24:0.12); 29.5 mg (0.05 mmol)

Polar organic solvent L1: acetonitrile; 10 mL

non-polar organic solvent L2: cyclohexane; 10 mL

CO ₂ -Pressure: 20 bar

After the reaction, the conversion of propargyl alcohol to the corresponding exo-vinylidenecarbonate was determined to be 30% by NMR. Extraction was performed with additional cyclohexane (3*10 mL). The silver content was 480 mg/kg in the non-polar organic phase and 30 mg/kg (Ρ = 16.0) after the first extraction and 5 mg/kg after the third extraction in the polar organic phase.

Example 10:

alkynol: propargyl alcohol (R ¹ =H); 280 mg (5 mmol)

silver salt: silver acetate [Ag(CH ₃ C(O)O)]; 8.3 mg (0.05 mmol)

Bulk donor ligands: compounds of formula V (actually obtained in 1.2, a mixture of V and W and unknown phosphine ligand in a ratio of approximately 1.0:0.24:0.12); 29.5 mg (0.05 mmol)

Polar organic solvent L1: acetonitrile; 10 mL

non-polar organic solvent L2: cyclohexane; 10 mL

CO ₂ -Pressure: 20 bar

After the reaction, the conversion of propargyl alcohol to the corresponding exo-vinylidenecarbonate was determined to be 50% by NMR. Extraction was performed with additional cyclohexane (3*10 mL). The silver content was 310 mg/kg in the non-polar organic phase and 90 mg/kg (Ρ = 3.4) after the first extraction and 32 mg/kg after the third extraction in the polar organic phase.

Example 11:

alkynol: propargyl alcohol (R ¹ =H); 280 mg (5 mmol)

Silver salt: silver neodecanoate [Ag(C ₉ H ₁₉ C(O)O)]; 14.0 mg (0.05 mmol)

Bulk donor ligands: compounds of formula W; 29.5 mg (0.05 mmol)

Polar organic solvent L1: acetonitrile; 10 mL

non-polar organic solvent L2: cyclohexane; 10 mL

CO ₂ -Pressure: 20 bar

After the reaction, the conversion of propargyl alcohol to the corresponding exo-vinylidenecarbonate was determined to be 36% by NMR. Extraction was performed with additional cyclohexane (3*10 mL). The silver content was 600 mg/kg in the non-polar organic phase and 21 mg/kg (Ρ = 28.6) after the first extraction and 2 mg/kg after the third extraction in the polar organic phase.

Example 12:

alkynol: propargyl alcohol (R ¹ =H); 280 mg (5 mmol)

Silver salt: silver neodecanoate [Ag(C ₉ H ₁₉ C(O)O)]; 14.0 mg (0.05 mmol)

Bulk donor ligands: compounds of formula W; 29.5 mg (0.05 mmol) ^*

Polar organic solvent L1: acetonitrile; 10 mL

non-polar organic solvent L2: cyclohexane; 10 mL

CO ₂ -pressure: 50 bar

After the reaction, the conversion of propargyl alcohol to the corresponding exo-vinylidenecarbonate was determined to be 81% by NMR. Upon recycle, the conversion to exo-vinylidenecarbonate was determined to be 70% by ¹ H NMR.

C. Substrate screening by addition of solvent L2 in carboxylation reaction:

An 80 mL steel autoclave was charged with propargyl alcohol (II), silver salt, bulky donor ligand, polar organic solvent CH ₃ CN and non-polar organic solvent cyclohexane. The reaction mixture was pressurized with CO ₂ and stirred at room temperature for 18 h. The CO ₂ overpressure was then carefully released. After phase separation, the conversion of propargyl alcohol in both phases and the formation of the product was determined by ¹ H-NMR spectroscopy. The silver content in both phases was determined by ICP-MS.

D. Recycle with addition of solvent L2 in the carboxylation reaction:

Example 21:

alkynol: compound II wherein R ¹ = —CH ₂ —O—CH ₂ —CH(OH)—CH ₂ —OC(CH ₃ ) ₃ ; 0.54 g (2.5 mmol)

Silver salt: silver neodecanoate [Ag(C ₉ H ₁₉ C(O)O)]; 7.0 mg (0.025 mmol)

bulky donor ligand: V; 14.7 mg (0.025 mmol)

Polar organic solvent L1: acetonitrile; 5 mL

non-polar organic solvent L2: cyclohexane; 2.5 mL

CO ₂ pressure: 20 bar

In a glove box, alkynol, silver(I) neodecanoate, Ligand V, acetonitrile and cyclohexane were placed in a Premex autoclave with Teflon insert. The autoclave was sealed and charged with 50 bar CO ₂ . After stirring at room temperature for 18 h, the CO ₂ pressure was carefully released, the autoclave was purged with argon, and then reintroduced into the glove box. Cyclohexane (2.5 mL) was added and the organic layer was separated with a separatory funnel. The acetonitrile layer was further washed with cyclohexane (2 x 5 mL). The combined cyclohexane washes were concentrated to approximately 2.5 mL and reintroduced into the autoclave, along with additional substrate and acetonitrile for subsequent runs. The post-treatment after the second run was the same as after the first run, and the whole procedure was repeated in the third run. The acetonitrile phase was treated with 1.25 M methanolic HCl (50 μ), filtered through a short path celite pad and the solvent removed under reduced pressure to provide the product. Product yield was determined by ¹ H-NMR using mesitylene as internal standard.

Yield of exo-vinylenecarbonate after first run: 90%

Yield of exo-vinylene carbonate after primary recycling: 81%

Yield of exo-vinylene carbonate after primary recycling: 71%

Claims (10)

A process for preparing a cyclic carbonate I selected from the group consisting of a compound of formula Ia, a compound of formula Ib, and mixtures thereof, comprising:

here
R ¹ is -CH ₂ -OR ¹⁴ ,
here
R ¹⁴ is hydrogen, C ₁ -C ₄ -alkyl bearing 1, 2 or 3 radicals R ¹⁵ ; -C(=O)R ¹⁶ and C ₃ -C ₆ -cycloalkyl bearing 1, 2 or 3 radicals R ¹⁷ ;
here
R ¹⁵ is selected from the group consisting of OH, C ₁ -C ₄ -alkoxy, phenyl and a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1 or 2 oxygen atoms as ring members; ;
R ¹⁶ is selected from the group consisting of C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₁ -C ₄ -alkoxy and —NR ¹⁸ R ¹⁹ , wherein R ¹⁸ is hydrogen or C ₁ -C ₄ -alkyl, R ¹⁹ is hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkyl substituted by the group R ²⁰ , and C ₁ -C ₄ -alkyl and C ₁ -C ₄ -alkoxy with selected from the group consisting of phenyl which may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of;
here
R ²⁰ is -OR ²¹ , -N(R ¹³ )-R ²¹ , -OC(=O)-R ²¹ , -C(=O)-OR ²¹ , -N(R ¹³ )-C(=O)- R ²¹ , -C(=O)-N(R ¹³ )-R ²¹ , -OC(=O)-OR ²¹ , -OC(=O)-N(R ¹³ )-R ²¹ , -N(R ¹³ ) )-C(=O)-OR ²¹ and -N(R ¹³ )-C(=O)-N(R ¹³ )-R ²¹ , wherein each R ²¹ is independently hydrogen, C ₁ -C ₆ -alkyl or C ₂ -C ₆ -alkenyl, wherein each R ¹³ is independently hydrogen or C ₁ -C ₁₀ -alkyl;
R ¹⁷ is -OR ²¹ , -N(R ¹³ )-R ²¹ , -OC(=O)-R ²¹ , -C(=O)-OR ²¹ , -N(R ¹³ )-C(=O)- R ²¹ , -C(=O)-N(R ¹³ )-R ²¹ , -OC(=O)-OR ²¹ , -OC(=O)-N(R ¹³ )-R ²¹ , -N(R ¹³ ) )-C(=O)-OR ²¹ and -N(R ¹³ )-C(=O)-N(R ¹³ )-R ²¹ , wherein each R ²¹ is independently hydrogen, C ₁ -C ₆ -alkyl or C ₂ -C ₆ -alkenyl, wherein each R ¹³ is independently hydrogen or C ₁ -C ₁₀ -alkyl;
A method comprising the steps of:
a) reacting propargyl alcohol of formula II with carbon dioxide:

wherein R ¹ is as defined above,
or the cyclic carbonate is a compound of formula I-bis:

wherein A is selected from the following bridging groups:
-CH ₂ -O-CH ₂ -1,4-phenylene-CH ₂ -O-CH ₂ -;
-CH ₂ -OC(=O)-NH-1,4-toluylene-NH-C(=O)-O-CH ₂ -;
-CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-(CH ₂ ) ₃ -O-CH ₂ -CH(OH)-CH ₂ -O-CH ₂ -;
-CH ₂ -O-CH ₂ -CH(OH)-CH ₂ -O-1,4-phenylene-C(CH ₃ ) ₂ -1,4-phenylene-O-CH ₂ -CH(OH)- CH ₂ —O—CH ₂ —; and
-CH ₂ -(OCH ₂ CH ₂ ) ₃ -O-CH ₂ -;
Propargyl alcohol is a compound of formula II, wherein R ¹ is —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is as defined above, or propargyl alcohol is a compound of formula II-bis:

wherein A is as defined above;
wherein the reaction is carried out in at least one organic solvent L1 or in a solvent mixture containing at least one organic solvent L1 and at least one organic solvent L2; wherein solvent L1 has a greater polarity than solvent L2, wherein solvents L1 and L2 have a miscibility gap at least at 20-30°C;
wherein the reaction is further carried out in the presence of a silver catalyst Ag1 comprising at least one bulky ligand and a carboxylate ligand,
wherein the bulky ligand is selected from compounds of formulas A to W and mixtures thereof:

wherein Me is methyl, Cy is cyclohexyl, i-Pr is isopropyl, Ph is phenyl, t-Bu is tert-butyl;
wherein the carboxylate ligand is according to formula (V):

here
R ⁶ is selected from the group consisting of C ₈ -C ₁₈ -alkyl and C ₂ -C ₄ -alkyl having a cyclohexyl ring;
b1) if step a) is not carried out in the presence of at least one solvent L2, adding solvent L2 to the reaction mixture obtained in step a); or
b2) if step a) is carried out in the presence of at least one solvent L2: optionally adding solvent L2 to the reaction mixture obtained in step a);
c) subjecting the reaction mixture obtained in step a), b1) or b2) to phase separation to obtain a product phase containing cyclic carbonate I and at least one solvent L1, and a silver catalyst and at least one solvent obtaining a catalyst phase containing L2; and
d), if desired, isolating the cyclic carbonate I from the product phase. 2 . The cyclic carbonate according to claim 1 , wherein the cyclic carbonate is compound Ia, compound Ib or mixtures thereof, wherein R ¹ is —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is —CH ₂ —CH(OH)—CH ₂ — OC(CH ₃ ) ₃ ; wherein propargyl alcohol is a compound of Formula II, wherein R ¹ is —CH ₂ —OR ¹⁴ , wherein R ¹⁴ is —CH ₂ —CH(OH)—CH ₂ —OC(CH ₃ ) ₃ . The process according to claim 1 or 2, wherein the silver catalyst Ag1 is used in step a) in an amount of 0.001 to 50 mol %, based on the amount of propargyl alcohol of formula (II). 4. The solvent according to any one of claims 1 to 3, wherein the solvent L1 is a polar aprotic solvent having a dipole moment of at least 10·10 ⁻³⁰ C·m;
Solvent L2 is a non-polar solvent having a dipole moment of up to 2·10 ^-30 C·m
Way. 5. The solvent according to any one of claims 1 to 4, wherein the solvent L1 is selected from the group consisting of amides, ureas, nitriles, sulfoxides, sulfones, carbonates, nitro compounds and mixtures thereof, and the solvent L2 is alkane, cyclo alkane and C ₁ -C ₂ -alkyl esters of C ₁₂ -C ₂₀ -fatty acids. 6. The method of claim 5, wherein solvent L1 is acetonitrile and solvent L2 is C ₅ -C ₁₄ -alkane, C ₁ -C ₂ -cycloalkane which may bear C ₁ -C ₂ -alkyl substituents, and saturated C ₁₂ -C ₂₀ selected from the group consisting of C ₁ -C ₂ -alkyl esters of fatty acids; or solvent L1 is dimethylformamide, solvent L2 is C ₅ -C ₁₄ -alkanes, C ₅ -C ₈ -cycloalkanes which may bear C ₁ -C ₂ -alkyl substituents, and saturated C ₁₂ -C ₂₀ fatty acids a method selected from the group consisting of C ₁ -C ₂ -alkyl esters of 6. The solvent according to claim 5, wherein the solvent L1 is a polar aprotic solvent and is formamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, N,N-dimethyl Imidazolinone, N,N-dimethylpropylene urea, acetonitrile, propionitrile, benzonitrile, dimethyl sulfoxide, sulfolane, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate , nitromethane, nitrobenzene and mixtures thereof;
solvent L2 is C ₅ -C ₁₅ -alkanes, C ₅ -C ₈ -cycloalkanes which may bear C ₁ -C ₂ -alkyl substituents, C ₁ -C ₂ -alkyl esters of C ₁₂ -C ₂₀ fatty acids and their which is selected from the group consisting of mixtures
Way. 8. The process according to claim 7, wherein the solvent L1 is acetonitrile and the solvent L2 is cyclohexane or decane. 9. The process according to any one of claims 1 to 8, wherein step a) is carried out at a pressure in the range from 0.1 to 200 bar and at a temperature in the range from 0 to 100°C. 10. The process according to any one of claims 1 to 9, wherein in step c) solvent L1 and solvent L2 are present in a total weight ratio of 80:20 to 20:80.